Water compatible sterically hindered alkoxyamines and hydroxy substituted alkoxyamines

ABSTRACT

Sterically hindered hydroxy substituted alkoxyamine stabilizer compounds are made water compatible via certain backbones with affinity towards water. The sterically hindered amines are for example of the formula (8)-(10) 
                         
These compounds are particularly effective in stabilizing aqueous polymer systems against the deleterious effects of oxidative, thermal and actinic radiation. The compounds are effective for example in stabilizing water borne coatings, aqueous inks, aqueous ink jet media and photocured aqueous systems.

This application is divisional of U.S. application Ser. No. 11/136,792,filed May 25, 2005, now U.S. Pat. No. 7,550,599, which is acontinuation-in-part of U.S. application Ser. No. 10/782,524, filed Feb.19, 2004, abandoned, which claims the benefit under 35 USC 119(e) ofU.S. provisional application No. 60/450,262, filed Feb. 26, 2003, thedisclosures of which are incorporated by reference.

The instant invention pertains to sterically hindered alkoxyamine andhydroxy substituted alkoxyamine stabilizer compounds which are watercompatible via certain backbones with affinity towards water. Thesematerials are particularly effective in stabilizing aqueous polymersystems against the deleterious effects of oxidative, thermal andactinic radiation. The compounds are effective for example instabilizing water borne coatings, aqueous inks, aqueous ink jet mediaand photocured aqueous systems.

U.S. Pat. Nos. 5,004,770 and 5,096,950 describe hindered amine compoundswhich are substituted on the N-atom by alkoxy moieties hereinincorporated by reference.

U.S. Pat. Nos. 6,271,377, 6,392,041 and 6,376,584 disclose stericallyhindered hydroxy substituted alkoxyamines herein incorporated byreference.

U.S. Pat. No. 6,254,724 teaches hindered hydroxylamine salt compoundsherein incorporated by reference.

U.S. Pat. No. 6,465,645 discloses long chain hindered amine stabilizersherein incorporated by reference.

U.S. Pat. Nos. 5,286,865 and 5,216,156 disclose non-migrating hinderedamine stabilizers herein incorporated by reference.

U.S. published app. No. 2002/0050226 and equivalent EP 1174476 disclosecertain hindered amines with certain water-soluble groups.

U.S. Pat. No. 6,102,997 discloses certain hindered amine compounds withwater solubilizing groups herein incorporated by reference.

JP2000044851 teaches an ink composition that contains certain hinderedamine compounds.

JP99170686 teaches hindered amine type additives generically in the inkreceiving layer of ink jet recording media.

US 2003/0070582 discloses ink compositions, recording media and an inkjet recording method stabilized with certain hindered amines hereinincorporated by reference.

U.S. Pat. No. 6,676,735 disclose aqueous ink compositions stabilizedwith certain hindered amines herein incorporated by reference.

U.S. Pat. No. 6,811,597 disclose ink compositions, recording media andan ink jet recording method stabilized with certain hindered aminesherein incorporated by reference.

US 2004/0011249 discloses ink compositions, recording media, and an inkjet recording method stabilized with certain hindered amines hereinincorporated by reference.

U.S. Pat. No. 6,719,833 disclose recording media and an image formingmethod stabilized with certain hindered amines herein incorporated byreference.

U.S. Pat. Nos. 5,457,204, 5,637,714, 5,665,885, and EP 0,634,399disclose organic materials stabilized against the damaging influence oflight, oxygen, and/or heat by certain hindered amines.

EP 0,413,665 discloses polymer stabilizers containing both hinderedamine and nitrone moieties.

U.S. Pat. No. 3,755,586 disclose anti-tussive compositions containingpiperidine derivatives.

EP 0,309,402 and EP 0,309,401 disclose certain hindered amines usefulfor the stabilization of polymer substrates.

JP 09,302,026 discloses certain hindered amines containingpolyallylamine polymers.

EP 0,389,419 discloses non-migrating 1-hydrocarbyloxy substitutedhindered amines as polymer stabilizers.

EP 0, 006,536 disclose piperidine-spiro-hydantoin derivatives and theiruse as light stabilizers for synthetic polymers.

EP 0,466,647, U.S. Pat. Nos. 5,160,346, and 5,281,707 disclose polyamidecompositions stabilized by water-soluble triazine derivatives ofhindered amines.

WO 2002/100,831 discloses 4-imino-N-alkoxy piperidine compounds andtheir use as polymerization regulators.

WO 2004/000,809 discloses cationic alkoxyamines and their use inproducing nano particles from natural or synthetic clays.

WO 2001/020, 078 disclose cationic nitroxides and hydroxylamine moietiesuseful for the stabilization of wood pulp and paper.

U.S. Pat. No. 6,102,997 and EP 0,882,600 disclose ink jet systems withimproved protection of the ink jet dyes from light.

The present compounds are sterically hindered alkoxyamines andsterically hindered hydroxy substituted alkoxyamines, which are madewater compatible or water-soluble with a water compatible orwater-soluble backbone.

The instant compounds perform extremely well in aqueous polymericsystems and polar high solids systems. The present compounds exhibitexcellent compatibility in polar environments such as polyurethane basedcoating systems, water borne automotive coating systems, polar recordingmedia and aqueous inks.

DETAILED DISCLOSURE

The present water compatible or water-soluble sterically hinderedalkoxyamines and hydroxy substituted alkoxyamines are of the formula(1)-(10)

where

E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atomsor aralkoxy of 7 to 15 carbon atoms, or E is —O-T-(OH)_(b),

T is a straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbonatoms, a straight or branched chain alkylene of 1 to 4 carbon atomssubstituted by phenyl or by phenyl substituted by one or two alkylgroups of 1 to 4 carbon atoms;

b is 1, 2 or 3 with the proviso that b cannot exceed the number ofcarbon atoms in T, and when b is 2 or 3, each hydroxyl group is attachedto a different carbon atoms of T;

E′ is hydrogen, C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₇-C₁₅-phenylalkyl,C₂-C₁₈alkanoyl or phenyl, or E′ is independently defined as for E,

R is hydrogen or methyl,

R₁ is hydrogen, C₁-C₁₂alkyl, C₅-C₈cycloalkyl, C₅-C₈cycloalkylsubstituted by one to three C₁-C₄alkyl, C₂-C₁₂alkenyl, phenyl,C₇-C₉phenylalkyl, glycidyl, C₂-C₁₂alkanoyl, C₆-C₉cycloalkylcarbonyl,C₂-C₁₂-carbamoyl, C₂-C₁₂alkenoyl, benzoyl, benzoyl substituted by one tothree C₁-C₄alkyl, C₂-C₁₂alkanoyl substituted by a di(C₁-C₆alkyl)phosphonate,

or R₁ is C₂-C₁₂alkyl, C₂-C₁₂alkanoyl or C₇-C₁₈phenylalkyl, eachinterrupted by one to six oxygen, sulfur or —N(R₆)— groups; C₁-C₁₂alkyl,C₂-C₁₂alkanoyl, phenyl or C₇-C₁₈phenylalkyl, each substituted by one tosix hydroxy groups or by one to six —NHR₆ groups; C₂-C₁₂alkyl,C₂-C₁₂alkanoyl or C₇-C₁₈phenylalkyl, each interrupted by one to three—NR₆C(O)— groups; or C₁-C₁₂alkyl, C₂-C₁₂alkanoyl, phenyl orC₇-C₁₈phenylalkyl, each substituted by one to three —SO₃H groups or byone to three —COOR₆ groups; or

R₁ is said alkyl substituted by a piperazine or by a morpholine group;or

R₁ is said interrupted group further substituted by one to six hydroxygroups or by one to six —NHR₆ groups; or

R₁ is said interrupted group further substituted by one to three —SO₃Hgroups or by one to three —COOR₆ groups;

or R₁ is a mono-valent homo- or co-oligomer consisting of monomer unitsderived from monomers selected from the group consisting of ethyleneoxide, propylene oxide, ethylene glycol, propylene glycol, acrylic acid,methacrylic acid, ethylene imine, acrylamide, vinyl formamide, vinylalcohol and vinyl acetate; which homo- or co-oligomer consists ofbetween 2 and about 24 monomer units;

R₁′ is independently defined as for R₁,

R₅ is a divalent homo- or co-oligomer consisting of monomer unitsderived from monomers selected from the group consisting of ethyleneoxide, propylene oxide, ethylene glycol, propylene glycol, acrylic acid,methacrylic acid, ethylene imine, acrylamide, vinyl formamide, vinylalcohol and vinyl acetate; which homo- or co-oligomer consists ofbetween 2 and about 24 monomer units,

R₆ is hydrogen or C₁-C₆alkyl,

R₆′ and R₆″ are independently defined as for R₆,

R₇ is —N(R₂)(R₂′) or is chlorine, alkoxy of 1 to 12 carbon atoms,2-hydroxyethylamino or —N(R₆)(R₆′);

or R₇ is

R₈ is defined as for R₇, where one of R₇ and R₈ is —N(R₂)(R₂′);

q is 2 to 8;

X⁻ is an inorganic or organic anion,

Y⁺ is a mono-, di- or tri-valent cation, and

when E is —O-T-(OH)_(b),

R₂ is glycidyl, C₂-C₁₂alkanoyl substituted by a di(C₁-C₆alkyl)phosphonate, or

R₂ is C₂-C₁₂alkyl, C₂-C₁₂alkanoyl or C₇-C₁₈phenylalkyl, each interruptedby one to six oxygen, sulfur or —N(R₆)— groups; C₁-C₁₂alkyl,C₂-C₁₂alkanoyl, phenyl or C₇-C₁₈phenylalkyl, each substituted by one tosix hydroxy groups or by one to six —NHR₆ groups; C₂-C₁₂alkyl,C₂-C₁₂alkanoyl or C₇-C₁₈phenylalkyl, each interrupted by one to three—NR₆C(O)— groups; or R₂ is C₁-C₁₂alkyl, C₂-C₁₂alkanoyl, phenyl orC₇-C₁₈phenylalkyl, each substituted by one to three —SO₃H groups or byone to three —COOR₆ groups; or

R₂ is said alkyl substituted by a piperazine or by a morpholine group;or

R₂ is said interrupted group further substituted by one to six hydroxygroups or by one to six —NHR₆ groups; or

R₂ is said interrupted group further substituted by one to three —SO₃Hgroups or by one to three —COOR₆ groups; or

R₂ is C₁-C₁₂alkyl, C₂-C₁₂alkanoyl, phenyl or C₇-C₁₈phenylalkyl, eachsubstituted by one or two —COO⁻Y⁺, —N(R₆)(R₆′)(R₆)″⁺X⁻ or —SO₃ ⁻Y⁺groups; or

R₂ is said C₁-C₁₂alkyl, C₂-C₁₂alkanoyl, phenyl or C₇-C₁₈phenylalkyl,each of which is substituted by one or two —COO⁻Y⁺, —N(R₆)(R₆′)(R₆″)⁺X⁻or —SO₃ ⁻Y⁺ groups, each further substituted by one or two —OH, —COOR₆or —NHR₆ groups; or

R₂ is a mono-valent homo- or co-oligomer consisting of monomer unitsderived from monomers selected from the group consisting of ethyleneoxide, propylene oxide, ethylene glycol, propylene glycol, acrylic acid,methacrylic acid, ethylene imine, acrylamide, vinyl formamide, vinylalcohol and vinyl acetate; which homo- or co-oligomer consists ofbetween 2 and about 24 monomer units,

R₂′ is defined as for R₂ and may also be hydrogen,

R₃ is defined as for R₂ and may also be —SO₃H, —PO₃H₂, —SO₃ ⁻Y⁺ or—PO₃H⁻Y⁺, and

R₄ is defined as for R₂ and may also be hydrogen,

and

when E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbonatoms or aralkoxy of 7 to 15 carbon atoms,

R₂ is C₁-C₁₂alkyl, C₂-C₁₂alkanoyl, phenyl or C₇-C₁₈phenylalkyl, eachsubstituted by one or two —COO⁻Y⁺, —N(R₆)(R₆′)⁺X⁻ or —SO₃ ⁻Y⁺ groups; or

R₂ is said C₁-C₁₂alkyl, C₂-C₁₂alkanoyl, phenyl or C₇-C₁₈phenylalkyl,each of which is substituted by one or two —COO⁻Y⁺, —N(R₆)(R₆′)⁺X⁻ or—SO₃ ⁻Y⁺ groups, each further substituted by one or two —OH, —COOR₆ or—NHR₆ groups, with the proviso that the compound

is not included; or

R₂ is a mono-valent homo- or co-oligomer consisting of monomer unitsderived from monomers selected from the group consisting of ethyleneoxide, propylene oxide, ethylene glycol, propylene glycol, acrylic acid,methacrylic acid, ethylene imine, acrylamide, vinyl formamide, vinylalcohol and vinyl acetate; which homo- or co-oligomer consists ofbetween 2 and about 24 monomer units;

R₂′ is defined as for R₂ and may also be hydrogen,

R₃ is defined as for R₂ and may also be —SO₃H, —PO₃H₂, —SO₃ ⁻Y⁺ or—PO₃H⁻Y⁺, and

R₄ is defined as for R₂ and may also be hydrogen.

For example, E is —O-T(OH)_(b).

For example, E is 2-hydroxycyclohexyloxy or 2-hydroxy-2-methylpropoxy.

For example, the present compounds are of the formula

where

E is —O-T(OH)_(b),

R₁ is hydrogen, C₁-C₆alkyl, C₂-C₆alkanoyl, C₂-C₆alkyl or C₂-C₆alkanoylinterrupted by one or two oxygen, sulfur or —N(R₆)— groups; C₁-C₆alkylor C₂-C₆alkanoyl substituted by one to three hydroxy groups or by one tothree —NHR₆ groups, C₂-C₆alkyl or C₂-C₆alkanoyl interrupted by a—NR₆C(O)— group, or is C₁-C₆alkyl or C₂-C₆alkanoyl substituted by a—SO₃H or by a —COOR₅ group, and

the other moities are as previously described.

For example, the present compounds are of the formula

where

E is —O-T(OH)_(b),

R₁ is hydrogen, C₁-C₄alkyl, C₂-C₅alkanoyl, C₂-C₄alkyl or C₂-C₅alkanoylinterrupted by an oxygen, sulfur or —N(R₆)— group; C₁-C₄alkyl orC₂-C₅alkanoyl substituted by an hydroxy group or by a —NHR₆ group,C₂-C₄alkyl or C₂-C₅alkanoyl interrupted by a —NR₆C(O)— group, or isC₁-C₄alkyl or C₂-C₅alkanoyl substituted by a —SO₃H or by a —COOR₆ group,

and the other moieties are as described previously.

For instance, the present compounds are of the formula

where

E is —O-T(OH)_(b),

R₂ and R₃ are C₂-C₆alkyl or C₂-C₆alkanoyl interrupted by one or twooxygen, sulfur or —N(R₆)— groups; C₁-C₆alkyl or C₂-C₆alkanoylsubstituted by one to three hydroxy groups or by one to three —NHR₆groups, C₂-C₆alkyl or C₂-C₆alkanoyl interrupted by a —NR₆C(O)— group, orR₂ is C₁-C₆alkyl or C₂-C₆alkanoyl substituted by a —SO₃H group or by a—COOR₆ group; or

R₂ and R₃ are C₁-C₆alkyl, C₂-C₆alkanoyl or C₇-C₉phenylalkyl, eachsubstituted by a —COO⁻Y⁺, —N(R₆)(R₆′)⁺X⁻ or —SO₃ ⁻Y⁺ group, and

the other moieties are as described previously.

For instance, the present compounds are of the formula

where

E is —O-T(OH)_(b),

R₂ and R₃ are C₂-C₄alkyl or C₂-C₅alkanoyl interrupted by an oxygen,sulfur or —N(R₆)— group; C₁-C₄alkyl or C₂-C₅alkanoyl substituted by anhydroxy group or by a —NHR₆ group, C₂-C₄alkyl or C₂-C₅alkanoylinterrupted by a —NR₆C(O)— group, or R₂ is C₁-C₄alkyl or C₂-C₅alkanoylsubstituted by a —SO₃H group or by a —COOR₆ group; or

R₂ and R₃ are C₁-C₄alkyl or C₂-C₅alkanoyl substituted by a —COO⁻Y⁺,—N(R₆)(R₆′)⁺X⁻ or —SO₃ ⁻Y⁺ group, and

the other moieties are as described previously.

For example, the present compounds are of the formula

where

E is —O-T(OH)_(b),

R₄ is hydrogen, C₂-C₆alkyl or C₂-C₆alkanoyl interrupted by one or twooxygen, sulfur or —N(R₆)— groups; C₁-C₆alkyl or C₂-C₆alkanoylsubstituted by one to three hydroxy groups or by one to three —NHR₆groups, C₂-C₆alkyl or C₂-C₆alkanoyl interrupted by a —NR₆C(O)— group, orR₄ is C₁-C₆alkyl or C₂-C₆alkanoyl substituted by a —SO₃H group or by a—COOR₆ group; or

R₄ is C₁-C₆alkyl, C₂-C₆alkanoyl or C₇-C₉phenylalkyl, each substituted bya —COO⁻Y⁺, —N(R₆)(R₆′)⁺X⁻ or —SO₃ ⁻Y⁺ group, and

the other moieties are as described previously.

For example, the present compounds are of the formula

where

E is —O-T(OH)_(b),

R₄ is hydrogen, C₂-C₄alkyl or C₂-C₅alkanoyl interrupted by an oxygen,sulfur or —N(R₆)— group; C₁-C₄alkyl or C₂-C₅alkanoyl substituted by anhydroxy group or by a —NHR₆ group, C₂-C₄alkyl or C₂-C₅alkanoylinterrupted by a —NR₆C(O)— group, or R₄ is C₁-C₄alkyl or C₂-C₅alkanoylsubstituted by a —SO₃H group or by a —COOR₆ group; or

R₄ is C₁-C₄alkyl or C₂-C₅alkanoyl substituted by a —COO⁻Y⁺,—N(R₆)(R₆′)⁺X⁻ or —SO₃ ⁻Y⁺ group, and

the other moities are as described previously.

For instance, the present compounds are of the formula

where

E is —O-T(OH)_(b),

R₅ is polyethylene glycol or polypropylene glycol, and

the other moities are as described previously.

For example, the present compounds are of the formula

where

E is —O-T(OH)_(b), and

where R_(x) is selected from the group consisting of

—NH₂ ⁺CH₂CH₂OHCl⁻, —NHCH₂CH₂OH, —NH₃ ⁺⁻OAc, ═NOH, —NHCH(CH₃)COO⁻K⁺,—NHCH₂CH₂N(CH₃)₂ ⁺⁻OAc, —NHCH₂CH₂SO₃ ⁻K⁺, —NHCH(COO⁻K⁺)CH₂CH₂SCH₃,—NHCH₂COO⁻K⁺, —NHCOCH₂OH, —NHCOCH₂NHCOCH₃, —NHCH₂CH₂CH₂SO₃H, —OCH₂CH₂OH,—OCH(CH₃)COO⁻K⁺, —OCH₂CH₂N(CH₃)₂ ⁺⁻OAc, —OCH₂CH₂SO₃ ⁻K⁺,—OCH(COO⁻K⁺)CH₂CH₂SCH₃, —OCH₂COO⁻K⁺, —OCOCH₂OH, —OCOCH₂NHCOCH₃ and—OCH₂CH₂CH₂SO₃H; and

where R_(y) is selected from the group consisting of

—NHCH₂CH₂NHCH₂CH₂NHCH₂CH₂NH₂, —NH₂ ⁺CH₂CH₂NHCH₂CH₂NHCH₂CH₂NH₂ ⁻OAc,—NHPhSO₃H, —NHPhSO₃ ⁻K⁺, —NHPhSO₃ ⁻Na⁺, —NH₂ ⁺PhSO₃HCl⁻,—NH(3-carboxy-4-chlorophenyl), —NH(3-COO⁻Na⁺-4-chlorophenyl),—NHCH₂CH₂—(N-piperazine), —NH₂ ⁺CH₂CH₂—(N-piperazine)⁻OAc and —NH₂⁺CH₂CH₂—(N-piperazine)⁻Cl.

For example, E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12carbon atoms or aralkoxy of 7 to 15 carbon atoms.

For instance, E is benzyloxy, methoxy, propoxy, butoxy, pentoxy,hexyloxy, heptyloxy, octyloxy or cyclohexyloxy.

For example, the present compounds are of the formula

where

E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atomsor aralkoxy of 7 to 15 carbon atoms,

R₁ is hydrogen, C₁-C₆alkyl, C₂-C₆alkanoyl, C₂-C₆alkyl or C₂-C₆alkanoylinterrupted by one or two oxygen, sulfur or —N(R₆)— groups; C₁-C₆alkylor C₂-C₆alkanoyl substituted by one to three hydroxy groups or by one tothree —NHR₆ groups, C₂-C₆alkyl or C₂-C₆alkanoyl interrupted by a—NR₆C(O)— group, or is C₁-C₆alkyl or C₂-C₆alkanoyl substituted by a—SO₃H or by a —COOR₆ group, and

the other moieties are as described previously.

For example, the present compounds are of the formula

where

E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atomsor aralkoxy of 7 to 15 carbon atoms,

R₁ is hydrogen, C₁-C₄alkyl, C₂-C₅alkanoyl, C₂-C₄alkyl or C₂-C₅alkanoylinterrupted by an oxygen, sulfur or —N(R₆)— group; C₁-C₄alkyl orC₂-C₅alkanoyl substituted by an hydroxy group or by a —NHR₆ group,C₂-C₄alkyl or C₂-C₅alkanoyl interrupted by a —NR₆C(O)— group, or isC₁-C₄alkyl or C₂-C₅alkanoyl substituted by a —SO₃H or by a —COOR₆ group,and

the other moities are as described previously.

For instance, the present compounds are of the formula

where

E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atomsor aralkoxy of 7 to 15 carbon atoms,

R₂ and R₃ are C₁-C₆alkyl, C₂-C₆alkanoyl or C₇-C₉phenylalkyl, eachsubstituted by a —COO⁻Y⁺, —N(R₆)(R₆′)⁺X⁻ or —SO₃ ⁻Y⁺ group, and

the other moieties are as described previously.

For instance, the present compounds are of the formula

where

E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atomsor aralkoxy of 7 to 15 carbon atoms,

R₂ and R₃ are C₁-C₄alkyl or C₂-C₅alkanoyl substituted by a —COO⁻Y⁺,—N(R₆)(R₆′)⁺X⁻ or —SO₃ ⁻Y⁺ group, and

the other moities are as described previously.

For example, the present compounds are of the formula

where

E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atomsor aralkoxy of 7 to 15 carbon atoms,

R₄ is C₁-C₆alkyl, C₂-C₆alkanoyl or C₇-C₉phenylalkyl, each substituted bya —COO⁻Y⁺, —N(R₆)(R₆′)⁺X⁻ or —SO₃ ⁻Y⁺ group, and

the other moities are as described previously.

For example, the present compounds are of the formula

where

E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atomsor aralkoxy of 7 to 15 carbon atoms,

R₄ is C₁-C₄alkyl or C₂-C₅alkanoyl substituted by a —COO⁻Y⁺,—N(R₆)(R₆′)⁺X⁻ or —SO₃ ⁻Y⁺ group, and

the other moities are as described previously.

For instance, the present compounds are of the formula

where

E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atomsor aralkoxy of 7 to 15 carbon atoms,

R₅ is polyethylene glycol or polypropylene glycol, and

the other moities are as described previously.

For example the present compounds are of the formula

where

E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atomsor aralkoxy of 7 to 15 carbon atoms, and

R_(x) is selected from the group consisting of

—NH₂ ⁺CH₂CH₂OHCl⁻, —NH₃ ⁺⁻OAc, ═NOH, —NHCH(CH₃)COO⁻K⁺, —NHCH₂CH₂N(CH₃)₂⁺⁻OAc, —NHCH₂CH₂SO₃ ⁻K⁺, —NHCH(COO⁻K⁺)CH₂CH₂SCH₃, —NHCH₂COO⁻K⁺,—OCH(CH₃)COO⁻K⁺, —OCH₂CH₂N(CH₃)₂ ⁺⁻OAc, —OCH₂CH₂SO₃ ⁻K⁺,—OCH(COO⁻K⁺)CH₂CH₂SCH₃ and —OCH₂COO⁻K⁺ and

where R_(y) is selected from the group consisting of

—NHCH₂CH₂NHCH₂CH₂NHCH₂CH₂NH₂, —NH₂ ⁺CH₂CH₂NHCH₂CH₂NHCH₂CH₂NH₂ ⁻OAc,—NHPhSO₃H, —NHPhSO₃ ⁻K⁺, —NHPhSO₃ ⁻Na⁺, —NH₂ ⁺PhSO₃HCl⁻,—NH(3-carboxy-4-chlorophenyl), —NH(3-COO⁻Na⁺-4-chlorophenyl),—NHCH₂CH₂—(N-piperazine), —NH₂ ⁺CH₂CH₂—(N-piperazine)⁻OAc and —NH₂⁺CH₂CH₂—(N-piperazine)⁻Cl.

The solubility of the present sterically hindered amines in water at 20°C. and standard pressure is for example greater than or equal to 1 g/L,for example ≧2 g/L, ≧5 g/L, ≧10 g/L, ≧20 g/L, ≧30 g/L, ≧40 g/L, ≧50 g/L,≧60 g/L, ≧70 g/L, ≧80 g/L, ≧90 g/L or ≧100 g/L.

Alkyl having up to 12 carbon atoms is branched or unbranched, and is forexample for example methyl, ethyl, propyl, isopropyl, n-butyl,sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl,1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl,isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl,n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl,nonyl, decyl, undecyl, 1-methylundecyl and dodecyl,1,1,3,3,5,5-hexamethylhexyl.

Alkenyl is an unsaturated version of alkyl, and is branched orunbranched, for example isopropenyl, propenyl, hexenyl, heptenyl, andthe like.

Unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl is, for example,cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl,methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl,tert-butylcyclohexyl, cycloheptyl or cyclooctyl. For example cyclohexyland tert-butylcyclohexyl.

C₁-C₄Alkyl-substituted phenyl, which contains for example 1 to 3, forinstance 1 or 2, alkyl groups, is, for example, o-, m- orp-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl,3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl,2-ethylphenyl or 2,6-diethylphenyl.

Phenylalkyl includes substituted phenylalkyl, for example phenylalkylsubstituted on the phenyl ring by from 1 to 3 C₁-C₄alkyl groups or from1 to 3 halogen or by a mixture thereof, and is for example, benzyl,4-chlorobenzyl, α-methylbenzyl, α,α-dimethylbenzyl, 2-phenylethyl,2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl,2,6-dimethylbenzyl or 4-tert-butylbenzyl.

Phenyl includes unsubstituted phenyl and phenyl substituted by from 1 to3 C₁-C₄ alkyl groups or from 1 to 3 halogen or by a mixture thereof.

Alkanoyl having up to 12 carbon atoms is branched or unbranched, and isfor example formyl, acetyl, propionyl, butanoyl, pentanoyl, hexanoyl,heptanoyl, octanoyl, nonanoyl, deca-noyl, undecanoyl or dodecanoyl.

C₆-C₉Cycloalkylcarbonyl is, for example, cyclopentylcarbonyl,cyclohexylcarbonyl, cycloheptylcarbonyl or cyclooctylcarbonyl.

Carbamoyl of up to 12 carbon atoms is branched or unbranched, and is forexample the carbamoyl equivalent of the alkanoyl groups, for examplebutamoyl, pentamoyl, hexamoyl and the like.

Alkenoyl of up to 12 carbon atoms is branched or unbranched, and is anunsaturated version of alkanoyl.

Benzoyl substituted by one to three C₁-C₄alkyl, is for example o-, m- orp-methylbenzoyl, 2,3-dimethylbenzoyl, 2,4-dimethylbenzoyl,2,5-dimethylbenzoyl, 2,6-dimethylbenzoyl, 3,4-dimethylbenzoyl,3,5-dimethylbenzoyl, 2-methyl-6-ethylbenzoyl, 4-tert-butylbenzoyl,2-ethylbenzoyl, 2,4,6-trimethylbenzoyl, 2,6-dimethyl-4-tert-butylbenzoylor 3,5-di-tert-butylbenzoyl.

C₂-C₂₅Alkanoyl substituted by a di(C₁-C₆alkyl)phosphonate group is, forexample, (CH₃CH₂O)₂POCH₂CO—, (CH₃O)₂POCH₂CO—, (CH₃CH₂CH₂CH₂O)₂POCH₂CO—,(CH₃CH₂O)₂POCH₂CH₂CO—, (CH₃O)₂POCH₂CH₂CO—, (CH₃CH₂CH₂CH₂O)₂POCH₂CH₂CO—,(CH₃CH₂O)₂PO(CH₂)₄CO—, (CH₃CH₂O)₂PO(CH₂)₈CO— or (CH₃CH₂O)₂PO(CH₂)₁₇CO—.

C₂-C₁₂Alkyl interrupted by oxygen, sulfur or by —N(R₆)— is, for example,CH₃—O—CH₂—, CH₃—S—CH₂—, CH₃—N(CH₃)—CH₂—, CH₃—O—CH₂CH₂—O—CH₂—,CH₃—(O—CH₂CH₂—)₂O—CH₂—, CH₃—(O—CH₂CH₂—)₃O—CH₂— orCH₃—(O—CH₂CH₂—)₄O—CH₂—.

C₃-C₁₂Alkanoyl interrupted by oxygen, sulfur or by —N(R₆)— is, forexample, CH₃—O—CH₂CO—, CH₃—S—CH₂CO—, CH₃—N(CH₃)—CH₂CO—,CH₃—O—CH₂CH₂—O—CH₂CO—, CH₃—(O—CH₂CH₂—)₂O—CH₂CO—,CH₃—(O—CH₂CH₂—)₃O—CH₂CO— or CH₃—(O—CH₂CH₂—)₄O—CH₂CO—.

Substitution by one to six also means of course by 1, 2, 3, 4, 5 or 6groups, if the length of the chain so allows. Substitution by one tothree means of course by 1, 2 or 3 groups, if the length of the chainallows.

Interruption by one to six groups means of course by 1, 2, 3, 4, 5 or 6groups, if length of the chain allows.

C₇-C₁₈Phenylalkyl interrupted by oxygen, sulfur or by —N(R₆)— andunsubstituted or substituted on the phenyl radical by from one to threeC₁-C₄alkyl groups is branched or unbranched, and is for examplephenoxymethyl, 2-methyl-phenoxymethyl, 3-methyl-phenoxymethyl,4-methyl-phenoxymethyl, 2,4-dimethyl-phenoxymethyl,2,3-dimethyl-phenoxymethyl, phenylthiomethyl,N-methyl-N-phenyl-aminomethyl, N-ethyl-N-phenyl-aminomethyl,4-tert-butyl-phenoxymethyl, 4-tert-butyl-phenoxyethoxy-methyl,2,4-di-tert-butyl-phenoxymethyl, 2,4-di-tert-butyl-phenoxyethoxymethyl,phenoxyethoxyethoxyethoxymethyl, benzyloxymethyl, benzyloxyethoxymethyl,N-benzyl-N-ethyl-aminomethyl or N-benzyl-N-isopropyl-aminomethyl.

The oligomers and co-oligomers of ethylene oxide, propylene oxide,ethylene glycol, propylene glycol, acrylic acid, methacrylic acid,ethylene imine, vinyl alcohol and vinyl acetate are of course oligomericand co-oligomeric versions of poly(ethylene oxide), poly(propyleneoxide), polyethylene glycol, polypropylene glycol, polyacrylic acid,polymethacrylic acid, poly(ethylene imine), polyacrylamide,polyvinylformamide, polyvinyl alcohol and polyvinyl acetate. Oligomersof the above, when mono-valent, may be capped with for example a methylgroup or an acetate group, for example the oligomers of polyethyleneglycol and polypropylene glycol. Homo- or co-oligomers between 2 andabout 24 monomer units are for example between 2 and 20 monomer units,between 2 and 17 monomer units, between 2 and 14 monomer units, between2 and 11 monomer units, between 2 and 9 monomer units, between 2 and 8monomer units, between 2 and 6 monomer units, between 2 and 5 monomerunits, or between 2 and 4 monomer units. The total number of carbonatoms in the oligomers and co-oligomers is for example less than 20.

X⁻ is an inorganic or organic anion, such as phosphate, phosphonate,carbonate, bicarbonate, nitrate, chloride, bromide, bisulfite, sulfite,bisulfate, sulfate, borate, formate, acetate (OAc), benzoate, citrate,oxalate, tartrate, acrylate, polyacrylate, fumarate, maleate, itaconate,glycolate, gluconate, malate, mandelate, tiglate, ascorbate,polymethacrylate, a carboxylate of nitrilotriacetic acid,hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraaceticacid or of diethylenetriaminepentaacetic acid, adiethylenetriaminepentamethylenephosphonate, an alkylsulfonate or anarylsulfonate. Of course, where it is for example a di-, tri- orquaternary valent anion, it forms ion pairs with 2, 3 or 4 cationsrespectively.

Y⁺ is a mono-, di- or tri-valent cation and is for example an alkalimetal cation, alkaline earth metal cation or aluminum cation. Forexample, Y⁺ is Na⁺, K⁺, Mg⁺⁺, Ca⁺⁺ or Al⁺⁺⁺. Of course, where it is adi- or tri-cation, it forms ion pairs with 2 or 3 anions respectively.

Also subject of the present invention are stabilized compositionscomprising

an organic material subject to the deleterious effects of light, heatand oxygen, and

an effective stabilizing amount of a present water compatible or watersoluble sterically hindered alkoxyamine or hydroxy substitutedalkoxyamine compound.

Another embodiment of the instant invention is a method for stabilizingink-jet prints, which comprises applying to a recording material forink-jet printing an ink composition containing a water soluble dye or asolution of a dye in an organic solvent and at least one compound of theformulae (1)-(10) as defined above and drying said recording material.

Another embodiment of the instant invention is a method for stabilizingink-jet prints, which comprises applying to a recording material forink-jet printing a casting or coating dispersion or an aqueous ororganic solution containing at least one compound of the formulae(1)-(10) as defined above and further applying either an ink compositioncontaining a water soluble dye or a solution of a dye in an organicsolvent; or an ink composition containing a water soluble dye or asolution of a dye in an organic solvent and at least one compound of theformulae (1)-(10) and drying said recording material.

The present water compatible or water soluble sterically hinderedalkoxyamines or hydroxy substituted alkoxyamine compounds areparticularly effective towards preventing color fading of compositionscomprising pigments or dyes.

Accordingly, colored compositions comprising pigments or dyes arestabilized compositions according to this invention. That is, thestabilized organic material is the pigment or dye.

The colored compositions are for example compositions comprising dyes,which compositions are selected from the group consisting of ink jetinks, ink jet recording media, coatings, body care products, householdproducts, textiles and fabrics.

The body care products, household products, textiles and fabrics are asdescribed in U.S. application No. 60/377,381, filed May 2, 2002,published as WO 03/103622, the disclosure of which is herebyincorporated by reference.

The body care products are for example hair care products such asshampoos or hair dyeing agents or dentrifices such as mouthwashes.

The present stabilized compositions are for example automotive coatingcompositions. Compositions to be stabilized including automotive coatingcompositions are disclosed for example in U.S. Pat. Nos. 5,977,219 and6,166,218, the disclosures of which are hereby incorporated byreference.

The acrylic resin lacquers which can be stabilized against light,moisture and oxygen in accordance to the instant invention are forexample acrylic resin stoving lacquers or thermosetting resins includingacrylic/melamine systems which are described, for example, in H.Kittel's “Lehrbuch and Beschichtungen”, Vol. 1, Part 2 on pages 735 and742 (Berlin 1972), “Lackkunstharze” (1977) by H. Wagner and H. F. Sarxon pages 229-238, and in S. Paul's “Surface Coatings: Science andTechnology”, (1985).

The polyester lacquers which can be stabilized against the action oflight and moisture are for instance stoving lacquers described e.g. inH. Wagner and H. F. Sarx, op. cit., on pages 86-99.

The alkyd resin lacquers which can be stabilized against the action oflight and moisture in accordance with the instant invention are forexample stoving lacquers which are used in particular for coatingautomobiles (automobile finishing lacquers), for example lacquers basedon alkyd/melamine resins and alkyd/acrylic/melamine resins (see H.Wagner and H. F. Sarx, “Lackkunstharze” (1977), pages 99-123). Othercrosslinking agents include glycoluril resins, blocked or unblockedisocyanates or epoxy resins. Other lacquers which can be stabilizedinclude those with crosslinkable functionalities such as carbamate andsiloxane.

The lacquers stabilized in accordance with the invention are suitableboth for metal finish coatings and solid shade finishes, especially inthe case of retouching finishes, as well as various coil coatingapplications. The lacquers stabilized in accordance with the inventionare preferably applied in the conventional manner by two methods, eitherby the single-coat method or by the two-coat method. In the lattermethod, the pigment-containing base coat is applied first and then acovering coat of clear lacquer over it.

In addition to acid-catalyzed baked finishes, it is also to be notedthat the compounds of the present invention are applicable for use innon-acid catalyzed thermoset resins such as epoxy, epoxy-polyester,vinyl, alkyd, acrylic and polyester resins, optionally modified withsilicon, isocyanates or isocyanurates. The epoxy and epoxy-polyesterresins are crosslinked with conventional crosslinkers such as acids,acid anhydrides, amines and the like. Correspondingly, the epoxide maybe utilized as the crosslinking agent for various acrylic or polyesterresin systems that have been modified by the presence of reactive groupson the backbone structure.

When used in two-coat finishes, the compounds of the instant inventioncan be incorporated in the clear coat or both in the clear coat and inthe pigmented base coat.

To attain maximum light stability, the concurrent use of otherconventional light stabilizers can be advantageous. Examples are UV(ultraviolet light) absorbers of the benzophenone, 2H-benzotriazole,acrylic acid derivatives, oxalanilide, aryl-s-triazine ormetal-containing types (e.g. organic nickel compounds). In two-coatsystems, these additional light stabilizers can be added to the clearcoat and/or the pigmented base coat.

When water soluble, water miscible or water dispersible coatings aredesired ammonium salts of acid groups present in the resin are formed.Powder coating compositions can be prepared by reacting glycidylmethacrylate with selected alcohol components.

The instant compounds are also useful in the stabilization of acidcatalyzed thermoset resins which are disclosed in U.S. Pat. No.5,112,890, the relevant parts of which are incorporated herein byreference.

These resins are used in baked enamels or stoving lacquers. Hinderedamine light stabilizers are well known to be effective in stabilizing ahost of organic substrates including polymers from the deleteriouseffects of oxygen and light. Such hindered amine light stabilizers havebeen used in the stabilization of hot-crosslinkable alkyd or acrylicmetallic stoving lacquers (see U.S. Pat. No. 4,426,472) and instabilizing acid-catalyzed stoving lacquers based on hot-crosslinkableacrylic polyester or alkyl resins (see U.S. Pat. Nos. 4,344,876 and4,426,471). None of the hindered amine light stabilizers of thesepatents possess the present water-solubilizing structures. The instantcompounds have such substitution.

In their industrial uses, enamels with high solids content based oncrosslinkable acrylic, polyester, urethane or alkyd resins are curedwith an additional acid catalyst. The present water compatible or watersoluble sterically hindered alkoxyamines and hydroxy substitutedalkoxyamines are suitable in such systems.

The acid catalyzed thermoset enamels must be stabilized in order tofunction acceptably in end-use applications. The stabilizers are neededto impart greater retention of durability to the cured enamels (asmeasured by 20° gloss, distinction of image, cracking or chalking); thestabilizers must not retard cure (normal bake for auto finishes at 121°C.; and low bake repair at 82° C.) as measured by hardness, adhesion,solvent resistance and humidity resistance; the enamel should not yellowon curing and further color change on exposure to light should beminimized.

The instant hindered amine light stabilizers fulfill each of theserequirements and provide alone or in combination with a UV absorberoutstanding light stabilization protection to the cured acid catalyzedthermoset enamels.

The instant invention also pertains to resin systems capable of beingfully cured under ambient conditions. For example, applicable resinsinclude alkyd, acrylic, polyester and epoxide resins as described in S.Paul's “Surface Coatings: Science and Technology” (1985), pages 70-310.Various acrylic and modified acrylic resins are described in H. Kittel's“Lehrbuch der Lacke unde Beschichtungen”, Vol. 1, Part 2, on pages 735and 742 (Berlin 1972), and in “Lack-kunstharze” (1977) by H. Wagner andH. F. Sarx, op. cit, on pages 229-238. Typical crosslinkable polyesterresins which can be stabilized against the action of light and moistureare described e.g. in H. Wagner and H. F. Sarx, op. cit., on pages86-99. The unmodified and modified alkyd resins which can be stabilizedare conventional resins which are used in trade sales, maintenance andautomotive refinish coatings. For example, such coatings are based onalkyd resins, alkyd/acrylic resins and alkyd/silicon reins (see H.Wagner and H. F. Sarx, op. cit., pages 99-123) optionally crosslinked byisocyanates or epoxy resins.

In addition various acrylic lacquer coating compositions are disclosedin U.S. Pat. No. 4,162,249. Other acrylic/alkyd resins withpolyisocyanate additives are disclosed in U.S. Pat. No. 4,471,083; andacrylic resins containing either pendant amino ester groups or glycidylgroups are described in U.S. Pat. No. 4,525,521.

The ambient cured coatings stabilized by the instant compounds aresuitable both for metal finish coatings and solid shade finishes,especially in the case of retouching finishes. The lacquers stabilizedby the instant compounds are preferably applied in a conventional mannerby two methods, either by the single-coat method or by the two-coatmethod. In the latter method, the pigment-containing base coat isapplied first and a covering coat of clear lacquer applied over it. Whenused in two-coat finishes, the instant hindered amine compound can beincorporated in the clear coat or both in the clear coat and in thepigmented base coat.

The instant invention also pertains to abrasion-resistant coatingcompositions suitable for coating over polycarbonates. Such coatings asdescribed in U.S. Pat. No. 5,214,085 comprise a silyl acrylate, aqueouscolloidal silica, a photoinitiator and optionally a polyfunctionalacrylate as well as UV absorbers. Such coatings provide resistance afterprolonged outdoor exposure to sunlight, moisture, thermal cyclingcausing yellowing, delamination and formation of microcracks anddecreasing transparency.

Related hindered amine stabilizers have been utilized individually andin combination with UV absorbers to improve the performancecharacteristics of ambient cured coating systems. Notwithstanding suchimprovements, there still exists a need to further retard thephotooxidation and photodegradation of such ambient cured systems andthereby provide increased effectiveness by maintaining the physicalintegrity of the coatings. Such effectiveness can be manifested byprevention of embrittlement, cracking, corrosion, erosion, loss ofgloss, chalking and yellowing of the coating.

It has now been determined that the aforementioned improvements can beachieved by the utilization of the present sterically hindered amines inambient cured coating systems as is taught in U.S. Pat. No. 5,124,378,the relevant parts of which are incorporated herein by reference. Inparticular, the physical integrity of the coatings is maintained to ahigher degree with significant reduction in loss of gloss and inyellowing. Accordingly, the instant invention relates to the use of thepresent sterically hindered alkoxyamines and hydroxy substitutedalkoxyamines, optionally together with further stabilizers, forstabilizing ambient cured coatings based on alkyd resins; thermosetacrylic resins; acrylic alkyds; acrylic alkyd or polyester resinsoptionally modified with silicon, isocyanates, isocyanurates, ketiminesor oxazolidines; and epoxide resins crosslinked with carboxylic acids,anhydrides, polyamines or mercaptans; and acrylic and polyester resinsystems modified with reactive groups in the backbone thereof andcrosslinked with epoxides; against the degradative effects of light,moisture and oxygen.

The instant invention also relates to electrodeposited coatings appliedto metal substrates where various top coats may be applied thereover.The inclusion of the instant compounds in the E-coat providesdelamination resistance to said E-coats. The primary resins in saidE-coats are acrylic or epoxy resins. These E-coats are described inEuropean patent application EP 0 576 943 A1.

The instant invention also pertains to water borne architecturalcoatings, for example, water borne latex emulsion paints.

The instant invention also pertains to ultraviolet light cured (UVcured) coating systems using unsaturated acrylic resins, polyurethaneacrylates, epoxy acrylates, polyester acrylates, unsaturatedpolyester/styrene resins and silyl acrylates.

Powder Coatings

The instant invention also pertains to powder coating formulations whichrequire resistance to photodegradation. Resin systems which would beapplicable include glycidyl methacrylate or acrylate-functional acrylicor acrylic hybrids, crosslinked with diacids or anhydrides; acid oranhydride functional acrylic or polyester resins crosslinked with TGIC;hydroxyl functional acrylic or polyester resins crosslinked withisocyanates. The stabilized coating may be a single layer applied to asubstrate, or may be a clearcoat applied over a water borne or solventborne basecoat.

The stabilized coating may also contain a UV absorber, consisting of oneof the aforementioned compounds.

Radiation-Cured Systems

The instant invention also pertains to radiation-cured coating systems.These systems comprise:

-   a. Ethylenically unsaturated polymerizable compounds-   b. At least one photoinitiator-   c. One or more of the instant stabilizing compounds

The coating composition may also include a UV absorbing stabilizer,represented by one of the classes mentioned.

The coating may also include pigments or other colorants designed toprovide opacity or aesthetic properties.

The ethylenically unsaturated polymerizable compounds can contain one ormore than one olefinic double bond. They may be low molecular(monomeric) or high molecular (oligomeric) compounds.

Typical examples of monomers containing one double bond are alkyl orhydroxyalkyl acrylates or methacrylates, for example methyl, ethyl,butyl, 2-ethylhexyl and 2-hydroxyethyl acrylate, isobornyl acrylate, andmethyl and ethyl methacrylate. Further examples of these monomers areacrylonitrile, acrylamide, methacrylamide, N-substituted(meth)acrylamides, vinyl esters such as vinyl acetate, vinyl ethers suchas isobutyl vinyl ether, styrene, alkylstyrenes, halostyrenes,N-vinylpyrrolidone, vinyl chloride and vinylidene chloride.

Examples of monomers containing more than one double bond are ethyleneglycol diacrylate, propylene glycol diacrylate, neopentyl glycoldiacrylate, hexamethylene glycol diacrylate, bisphenol A diacrylate,4,4′-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylolpropanetriacrylate, pentaerythritol triacrylate and tetraacrylate,pentaerythritol divinyl ether, vinyl acrylate, divinyl benzene, divinylsuccinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurateor tris(2-acryloylethyl)isocyanurate. Examples of high molecular weight(oligomeric) polyunsaturated compounds are acrylated epoxy resins,acrylated polyethers, acrylated polyurethanes and acrylated polyesters.Further examples of unsaturated oligomers are unsaturated polyesterresins, which are usually prepared from maleic acid, phthalic acid andone or more diols and which have molecular weights of greater than about500. Unsaturated oligomers of this type are also known as prepolymers.

Typical examples of unsaturated compounds are esters of ethylenicallyunsaturated carboxylic acids and polyols or polyepoxides, and polymerscontaining ethylenically unsaturated groups in the chain or in sidegroups, including unsaturated polyesters, polyamides and polyurethanesand copolymers thereof, polybutadiene and butadiene copolymers,polyisoprene and isoprene copolymers, polymers and copolymers containing(meth)acrylic groups in side-chains, as well as mixtures of one or morethan one such polymer.

Illustrative examples of unsaturated carboxylic acids are acrylic acid,methacrylic acid, crotonic acid, itaconic acid, cinnamic acid,unsaturated fatty acids such as linolenic acid or oleic acid. Acrylicand methacrylic acid are preferred.

Suitable polyols are aromatic and, preferably, aliphatic andcycloaliphatic polyols. Aromatic polyols are typically hydroquinone,4,4′-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane, as well asnovolacs and cresols. Polyepoxides include those based on the citedpolyols, preferably on the aromatic polyols and epichlorohydrin. Furthersuitable polyols are polymers and copolymers which contain hydroxylgroups in the polymer chain or in side groups, for example polyvinylalcohol and copolymers thereof or hydroxyalkyl polymethacrylates orcopolymers thereof. Other suitable polyols are oligoesters carryinghydroxyl end groups.

Illustrative examples of aliphatic and cycloaliphatic polyols arealkylenediols containing preferably 2 to 12 carbon atoms, includingethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol,pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol,triethylene glycol, polyethylene glycols having molecular weights ofpreferably 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3- or1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol,tris(□-hydroxyethyl)amine, trimethylolethane, trimethylolpropane,pentaerythritol, dipentaerythritol and sorbitol.

The polyols may be esterified partially or completely with one or withdifferent unsaturated carboxylic acids, in which case the free hydroxylgroups of the partial esters may be modified, for example etherified, oresterified with other carboxylic acids.

Illustrative examples of esters are: Trimethylolpropane triacrylate,trimethylolethane triacrylate, trimethylolpropane trimethacrylate,trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate,triethylene glycol dimethacrylate, tetraethylene glycol diacrylate,pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritoltetraacrylate, dipentaerythritol diacrylate, dipentaerythritoltriacrylate, dipentaerythritol tetraacrylate, dipentaerythritolpentacrylate, dipentaerythritol hexacrylate, tripentaerythritoloctacrylate, pentaerythritol dimethacrylate, pentaerythritoltrimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritoltetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritoldiitaconate, dipentaerythritol trisitaconate, dipentaerythritolpentaitaconate, dipentaerythritol hexaitaconate, ethylene glycoldiacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate,1,4-butanediol diitaconate, sorbitol triacrylate, sorbitoltetraacrylate, pentaerythritol-modified triacrylate, sorbitoltetramethacrylate, sorbitol pentacrylate, sorbitol hexacrylate,oligoester acrylates and methacrylates, glycerol di- and -triacrylate,1,4-cyclohexanediacrylate, bisacrylates and bismethacrylates ofpolyethylene glycol having molecular weights of 200 to 1500, or mixturesthereof. Polyfunctional monomers and oligomers are available for examplefrom UCB Chemicals, Smyrna, Ga,, and Sartomer, Exton, Pa.

Suitable ethylenically unsaturated polymerizable compounds are also theamides of identical or different unsaturated carboxylic acids ofaromatic, cycloaliphatic and aliphatic polyamines containing preferably2 to 6, more particularly 2 to 4, amino groups. Exemplary of suchpolyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3-or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine,octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane,isophoronediamine, phenylenediamine, bisphenylenediamine,bis(β-aminoethyl)ether, diethylenetriamine, triethylenetetramine,bis(β-aminoethoxy)ethane or bis(β-aminopropoxy)ethane. Other suitablepolyamines are polymers and copolymers which may contain additionalamino groups in the side-chain and oligoamides containing amino endgroups.

Exemplary of such unsaturated amides are: Methylenebisacrylamide,1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide,bis(methacrylamidopropoxy)ethane, β-methacrylamidoethylmethacrylate,N-[(β-hydroxyethoxy)ethyl]acrylamide.

Suitable unsaturated polyesters and polyamides are derived typicallyfrom maleic acid and diols or diamines. Maleic acid can be partiallyreplaced by other dicarboxylic acids such as fumaric acid, itaconicacid, citraconic acid, mesaconic acid or chloromaleic acid. To controlthe reactivity of the polyester and to influence the crosslinkingdensity and hence the product properties, it is possible to use inaddition to the unsaturated dicarboxylic acids different amounts ofsaturated dicarboxylic acids such as phthalic acid, isophthalic acid,terephthalic acid, tetrahydrophthalic acid, succinic acid or adipicacid. The unsaturated polyesters can be used together with ethylenicallyunsaturated comonomers such as styrene. The polyesters and polyamidescan also be derived from dicarboxylic acids and ethylenicallyunsaturated diols or diamines, especially from those with long chainscontaining typically from 6 to 20 carbon atoms. Polyurethanes aretypically those derived from saturated or unsaturated diisocyanates andunsaturated and saturated diols.

Suitable polyester acrylates or acrylated polyesters are obtained byreacting oligomers, typically epoxides, urethanes, polyethers orpolyesters, with acrylates such as hydroxyethyl acrylate orhydroxypropyl acrylate.

Polybutadiene and polyisoprene and copolymers thereof are known.Suitable comonomers include olefins such as ethylene, propene, butene,hexene, (meth)acrylates, acrylonitrile, styrene or vinyl chloride.Polymers containing (meth)acrylate groups in the side-chain are alsoknown. They may typically be reaction products of epoxy resins based onnovolak with (meth)acrylic acid, homo- or copolymers of polyvinylalcohol or their hydroxyalkyl derivatives which are esterified with(meth)acrylic acid or homo- and copolymers of (meth)acrylates which areesterified with hydroxyalkyl(meth)acrylates.

Preferred monomers are typically alkyl- or hydroxyalkyl acrylates ormethacrylates, styrene, ethylene glycol diacrylate, propylene glycoldiacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylateor bisphenol A diacrylate, 4,4′-bis(2-acryloyloxyethoxy)diphenylpropane,trimethylolpropane triacrylate, pentaerythritol triacrylate ortetraacrylate, preferably acrylates, styrene, hexamethylene glycol orbisphenol A diacrylate, 4,4′-bis(2-acryloyloxyethoxy)diphenylpropane ortrimethylolpropane triacrylate.

Particularly preferred (oligomeric) polyunsaturated compounds arepolyester acrylates or unsaturated polyester resins which are preparedfrom maleic acid, fumaric acid, phthalic acid and one or more than onediol, and which typically have molecular weights from about 500 to 3000.

Preferred unsaturated carboxylic acids are acrylic acid and methacrylicacid.

The photopolymerizable compounds are used by themselves or in anydesired mixtures. It is preferred to use mixtures ofpolyol(meth)acrylates.

Binders may also be added to the unsaturated photopolymerizablecompounds. The addition of binders is particularly useful if thephotopolymerizable compounds are liquid or viscous substances. Theamount of binder may be from 5-95, preferably 10-90 and, mostpreferably, 40-90, percent by weight, based on the entire composition.The choice of binder will depend on the field of use and the desiredproperties therefore, such as the ability of the compositions to bedeveloped in aqueous and organic solvent systems, adhesion to substratesand susceptibility to oxygen.

Suitable binders are typically polymers having a molecular weight ofabout 5,000 to 2,000,000, preferably 10,000 to 1,000,000. Illustrativeexamples are: Homo- and copolymers of acrylates and methacrylates,including copolymers of methyl methacrylate/ethyl acrylate/methacrylicacid, poly(alkylmethacrylates), poly(alkylacrylates); cellulose estersand ethers such as cellulose acetate, cellulose acetobutyrate, methylcellulose, ethyl cellulose; polyvinyl butyral, polyvinyl formal,cyclized rubber, polyethers such as polyethylene oxide, polypropyleneoxide, polytetrahydrofuran; polystyrene, polycarbonate, polyurethane,chlorinated polyolefins, polyvinyl chloride, copolymers of vinylchloride/vinylidene chloride, copolymers of vinylidene chloride withacrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate,copoly(ethylene/vinyl acetate), polymers such as polycaprolactam andpoly(hexamethylene adipamide), polyesters such as poly(ethylene glycolterephthalate) and poly(hexamethylene glycol succinate).

The unsaturated compounds can also be used in admixture withnon-photopolymerizable film-forming components. These components may bephysically drying polymers or solutions thereof in organic solvents, forexample nitrocellulose or cellulose acetobutyrate. Thephotopolymerizable unsaturated monomers may be a component of a freeradical-ionic curable blend, such as a free radical-cationic curableblend. Also of importance are systems that undergo both thermal andphoto-induced curing cycles, such as are used in powder coatings,laminates, certain adhesives and conformal coatings.

Mixtures of a prepolymer with polyunsaturated monomers which,additionally contain a further unsaturated monomer are frequently usedin paint systems. The prepolymer in this instance primarily determinesthe properties of the paint film and, by varying it, the skilled personcan influence the properties of the cured film. The polyunsaturatedmonomer acts as crosslinking agent that renders the paint filminsoluble. The mono-unsaturated monomer acts as reactive diluent withthe aid of which the viscosity is lowered without having to use asolvent. Moreover, properties of the cured composition such as curingrate, crosslinking density and surface properties are dependent on thechoice of monomer.

Unsaturated polyester resins are usually used in two-component systems,together with a mono-unsaturated monomer, preferably with styrene.

Binary electron-rich/electron-poor monomer systems are often employed inthick pigmented coatings. For example, vinyl ether/unsaturated polyestersystems are employed in powder coatings and styrene/unsaturatedpolyester systems are used in gel coats.

A preferred process is that wherein the ethylenically unsaturatedpolymerizable compounds are a mixture of (i) at least one oligomericcompound and (ii) at least one monomer.

An interesting process is that wherein the ethylenically unsaturatedpolymerizable compounds are a mixture of (i) unsaturated polyesters,especially those that are prepared from maleic acid, fumaric acid and/orphthalic acid and one or more than one diol, and which have molecularweights of 500 to 3,000, and (ii) acrylates, methacrylates or styrene orcombinations thereof.

An important process is also that wherein the ethylenically unsaturatedpolymerizable compounds are a mixture of (i) unsaturated polyesters and(ii) acrylates or methacrylates or combinations thereof.

Another interesting process is that wherein the ethylenicallyunsaturated polymerizable compounds are a mixture of (i) unsaturatedpolyester acrylates and (ii) acrylates or methacrylates or combinationsthereof.

The amount of instant stabilizer compounds employed in the compositionsof this invention are for example from about 0.001% to about 10% byweight, based on the weight of the composition and depending on thecomposition.

For example, the amount of the present stabilizers employed in body careproducts, household products, textiles and fabrics is from about 0.001%to about 10% by weight, or from about 0.001% to about 5% by weight,based on the weight of the composition.

The amount of instant stabilizer compounds employed in coatings is fromabout 0.1 to about 10% by weight, for example from about 0.2 to about 5%by weight, for example from about 0.5 to about 3% by weight based on theweight of the solvent-free binder. The binders can be dissolved ordispersed in customary organic solvents or in water or can besolvent-free.

If combinations of stabilizers are used, the sum of all lightstabilizers is for example from about 0.2 to about 20% by weight, forinstance from about 0.5 to about 5% by weight, based on the film-formingresin.

It is also contemplated that the instant compounds would find particularvalue when used with water soluble inks and related polar orientedutilities where the presence of the water solubilizing groups wouldprovide for better compatibility and properties related to such aqueousenvironments.

Other materials that are stabilized according to the instant inventioninclude recording materials such as photographic reproductions orreprographic materials. The novel recording materials also include, forexample, pressure-sensitive copying systems, microcapsule photocopiersystems, heat-sensitive copier systems, photographic material andink-jet printing. The various components of ink jet media are disclosedfor example in U.S. Pat. Nos. 4,503,111, 4,575,465, 4,935,307,5,206,071, 6,096,826 and 6,127,037 and U.S. app. No. 60/406,441, filedAug. 28, 2002, the relevant parts of which are hereby incorporated byreference.

The ink jet ink according to this invention comprises about 0.01 toabout 30% by weight, for example about 0.1 to about 20% by weight, of atleast one present sterically hindered amine stabilizer, based on theweight of the ink jet ink.

The ink jet recording material according to this invention comprisesabout 1 to about 10000 mg/m², for example about 50 to about 2000 mg/m²,of at least one present sterically hindered amine stabilizer.

The present sterically hindered amine stabilizers are preferably addedto casting or coating dispersions which are applied by customarytechniques to the support of the ink jet recording material, or they canbe absorbed onto the material from an aqueous or organic solution. Ifthe recording material contains more than one layer, the compoundsaccording to this invention can be added to one layer or can bedistributed over a plurality of layers, wherein they can be applied to aplurality of layers in the same or different concentrations.

The present sterically hindered amine stabilizers are preferably used inink jet inks or recording materials, but may also be incorporated in inkcompositions for felt-tipped pens, ink pads, fountain pens, and penplotters, as well as for offset, book, flexographic and intaglioprinting, and also for typewriter ribbons for dot matrix andcalligraphic printing. The sterically hindered amine stabilizers canfurther be used in silver halide photographic materials as well as inrecording materials for pressure-sensitive copying systems, microcapsulephotocopier systems, heat-sensitive copier systems, dye diffusiontransfer printing, thermal wax transfer printing and dot matrixprinting, and for use with electrostatic, electrographic,electrophoretic, magnetographic and laser-electrophotographic printers,recorders or plotters.

Amongst the printers used for ink jet printing, a distinction is usuallymade between continuous and drop-on-demand printers. The ink jet systemaccording to this invention is suited for use with both type ofprinters.

The ink compositions according to the novel ink jet system arepreferably water borne inks and may contain water soluble solvents suchas ethylene glycol, diethylene glycol, triethylene glycol or higherethylene glycols, propylene glycol, 1,4-butanediol, or ethers of suchglycols, thiodiglycol, glycerol and the ethers and esters thereof,polyglycerol, mono-, di- and triethanolamine, propanolamine, dimethylformamide, dimethyl sulfoxide, dimethyl acetamide, N-methylpyrrolidone,1,3-dimethylimidazolidone, methanol, ethanol, isopropanol, n-propanol,diacetone alcohol, acetone, methyl ethyl ketone or propylene carbonate.

The ink compositions according to the novel ink jet system preferablycontain water soluble dyes, such as those known for dyeing naturalfibres. These can, for example, be acid dyes, direct dyes, reactivedyes, mono-, di- or polyazo dyes, triphenylmethane dyes, xanthene dyesor phtalocyanine dyes. Specific examples of such dyes are Food Black 2,Direct Black 19, Direct Black 38, Direct Black 168, Sulphur Black 1,Acid Red 14, Acid Red 35, Acid Red 52, Acid Red 249, Direct Red 227,Reactive Red 24, Reactive Red 40, Reactive Red 120, Reactive Red 159,Reactive Red 180, Acid Yellow 17, Acid Yellow 23, Direct Yellow 86,Direct Yellow 132, Acid blue 9, Acid Blue 185, Direct Blue 86, DirectBlue 199, copper phtalocyanines and the azo dyes listed in EP-A-366 221.

The ink compositions according to the invention may be nonaqueous andconsist of a solution of dyes in an organic solvent or a mixture oforganic solvents. Examples of solvents used for this purpose are alkylcarbitols, alkylcellosolves, dialkylformamides, dialkylacetamides,alcohols, acetone, methylethylketone, diethylketone, methyl isobutylketone, diisopropyl ketone, dibutyl ketone, dioxane, ethyl butyrate,ethyl isovalerate, diethyl malonate, diethyl succinate, butyl acetate,triethyl phosphate, ethylglycol acetate, toluene, xylene, tetralin orpetroleum fractions. Example of solid waxes as solvents, which, as anink carrier, must first be heated, are stearic or palmiric acid. Solventbased inks contain dyes soluble therein, for example Solvent Red,Solvent Yellow, Solvent Orange, Solvent Blue, Solvent Green, SolventViolet, Solvent Brown or Solvent Black.

The ink compositions according to the novel ink jet system may alsocontain minor amounts of conventional modifiers such as binders,surfactants, biocides, corrosion inhibitors, sequestrants, pH buffers orconductivity additives. They may also contain further light stabilizersor UV absorbers, including the compounds disclosed in U.S. Pat. Nos.5,073,448, 5,089,050, 5,096,489, 5,124,723, 5,098,477 and 5,509,957.

The ink compositions according to the invention may also consist of morethan one phase. Ink compositions that consist of an aqueous phase inwhich the dye is dissolved and a dispersed oil phase that contains an UVabsorber and/or an antioxidant are for example disclosed in JP-A-01170675, JP-A-01182 379, JP-A-01182 380, JP-A-01182 381, JP-A-01193 376. Oilsoluble dyes can be dissolved in an oil together with UV absorbersand/or antioxidants. The oil is either emulsified or dispersed in anaqueous phase as described, inter alia, in JP-A-01170674 andJP-A-01170672.

Further suited ink jet ink compositions are described in EP-A-672 538,pages 3 to 6.

The recording materials according to the novel ink jet system consist ofa substrate having a surface which is printable by means of an ink jet.The substrate is usually plain paper or polyolefin-laminated paper or aplastic sheet and is usually coated with at least one layer which isable to absorb ink. The substrate preferably has a thickness of 80 to250 μm.

Uncoated paper might also be used. In this case, the paper actssimultaneously as substrate and ink absorbing layer. Materials made ofcellulosic fibers and textile fibers materials such as cotton fabrics orblends of cotton and polyacrylamide or polyester, which might containthe present sterically hindered amine light stabilizers, can also beused as printing materials.

The recording materials may also be transparent, as in the case ofoverhead projection transparencies.

The present sterically hindered amine stabilizers can be incorporated inthe substrate during production thereof, conveniently by addition to thepulp during paper manufacture. Another method of application consists inspraying the substrate with a solution of the present stericallyhindered amine stabiilzers in water or in a readily volatile organicsolvent. The use of emulsions or dispersions is also possible.

Usually, however, at least one coating composition with high dyeaffinity is coated onto the substrate and, in this case, the presentsterically hindered amines are added to at least one of the said coatingcompositions. Typical coating compositions comprise, for example, asolid filler, a binder and conventional additives.

Example of suitable fillers are SiO₂, kaolin, talc, clay, calciumsilicate, magnesium silicate, aluminium silicate, gypsum, zeolites,bentonite, diatomaceous earth, vermiculite, starch or the surfacemodified SiO₂ described in JP-A-60 260 377. Small amounts of whitepigments, for example titanium dioxide, barytes, magnesium oxide, lime,chalk or magnesium carbonate, can be used with the filler in the coatingcomposition, provided they do not significantly lower the print densityof the ink jet prints.

The present sterically hindered amines may advantageously be employed ina nanoporous or microporous ink jet material.

Coating compositions which are intended for transparent, projectablerecording materials must not contain any light-scattering particles,such as pigments and fillers.

The binder binds the fillers to one another and to the substrate.Typical conventional binders are water soluble polymers such aspolyvinyl alcohol, partially hydrolysed polyvinyl acetate, cellulose andcellulose derivatives such as hydroxyethyl cellulose, polyvinylpyrrolidone and copolymers thereof, polyethylene oxide, salts ofpolyacrylic acid, sodium alginate, starch and starch derivatives, Naalginate, polyethylene imine, polyvinylpyridinium halide, gelatines andgelatine derivatives such as phthaloyl gelatines, casein, vegetable gum,dextrin, albumin, dispersions and polyacrylates or acrylate/methacrylatecopolymers, lattices of natural or synthetic rubber,poly(meth)acrylamide, polyvinyl ethers, polyvinyl esters, copolymers ofmaleic acid, melamine resins, urea resins, water soluble polyurethanesand polyesters, or the chemically modified polyvinyl alcohols disclosedin JP-A-61 134 290 or JP-A-61 134 291.

An additional dye receptor or a mordant which enhances the fixation ofthe dye to the coating may be added to the binder. Dye receptors foracid dyes are cationic or amphoteric. The cationic mordants can besoluble or dispersible in water. Exemplary cationic mordants arepolymeric ammonium compounds such as polyvinylbenzyldi- ortrialkylammonium compounds, optionally quaternized poly(di)allylammoniumcompounds, polymeth-acryloxyethyldimethylhydroxyethylammonium chloride,polyvinyl benzyl methylimidazolium chloride, polyvinylbenzylpicoliniumchloride or polyvinylbenzyltributylammonium chloride. Further examplesare basic polymers such as poly(dimethylaminoethyl)methacrylate,polyalkylenepolyamines and their condensation products withdicyanodiamide, amine/epichlorohydrin polycondensates or the compoundsdisclosed in JP-A-57-36692, 57-64591, 57-187289, 57-191084, 58-177390,58-208357, 59-20696, 59-33176, 59-96987, 59-198188, 60-49990, 60-71796,60-72785, 60-161188, 60-187 582, 60-189481, 60-189482, 61-14979,61-43593, 61-57379, 61-57380, 61-58788, 61-61887, 61-63477, 61-72581,61-95977, 61-134291 or in U.S. Pat. Nos. 4,547,405 and 4,554,181 as wellas in DE-A-3417582 and EP-B-609 930. The mordants used can also becompounds containing phosphonium groups (EP-B-609 930) as well as groundcationic ion exchange resins which are introduced in the mordant layerin a finely divided form. Further suitable cationic mordants aredescribed in U.S. Pat. No. 6,102,997, pages 12 to 17. The cationicmordants can be soluble or dispersible in water and have an averagemolecular weight (weight average) of preferably at least 2,000 and, inparticular, at least 20,000.

Besides the dye acceptor layer(s), the ink jet recording material mightcomprise other layers on the ink receiving side, which are intended, forexample, for providing scratch resistance, absorbing water orcontrolling whiteness and/or glossiness. The backside of the substratemight also be coated with at least one binder layer, in order to preventbuckling of the recording material.

The ink jet recording material might also contain a number of otheradditives such as antioxidants, further light stabilizers (alsoincluding UV absorbers), viscosity improvers, fluorescent whiteningagents, biocides, wetting agents, emulsifiers and spacers.

Suitable spacers are in particular spherical, have an average diameterof 1 to 50 μm, and in particular 5 to 20 μm, and have a narrow particlesize distribution. Suitable spacers consist, for example, ofpolymethylmethacrylate, polystyrene, polyvinyl toluene, silicon dioxideand insoluble starch.

Illustrative examples of particularly suitable antioxidants aresterically hindered phenols, hydroquinones and hydroquinone ethers, forexample the antioxidants disclosed in GB-A-2 088 777 or JP-A-60-72785,JP-A-0-72786 and JP-A-60-71796.

Illustrative examples of particularly suitable light stabilizers areorganic nickel compounds and sterically hindered amines, for example thelight stabilizers disclosed in JP-A-58-152072, 61-146591, 61-163886,60-72785 and 61-146591 or in EP 373 573, 685 345 and 704 316, GB-A-2 088777, JP-A-59-169883 and 61-177279.

Suitable UV absorbers are disclosed, inter alia, in Research DisclosureNo. 24239 (1984) page 284, 37254 part VIII (1995) page 292, 37038 part X(1995) page 85 and 38957 part VI (1996), GB-A-2 088 777, EP 280 650, EP306 083 and EP 711 804. These compounds are preferably introduced intothe layer(s) farthest from the support. In a particular embodiment, theUV absorbers are contained in a layer above the layer(s) containing thepresent sterically hindered amines. Suitable UV absorbers for concurrentuse with a present sterically hindered amines in recording materials forink jet printing are in particular those of the2′-hydroxyphenyl-benzotriazole and 2′-hydroxyphenyltriazine class and,most particularly, 2-(2′-hydroxy-3′,5′-di-tert-amylphenyl)benzotriazoleand2-(2′-hydroxy-3′-tert-butyl-5′-polyglycolpropionate-phenyl)benzotriazole.Further examples of particularly suited UV absorbers are listed in U.S.Pat. No. 6,102,997 pages 18-19. The UV absorbers can be soluble orinsoluble in water and added to the coating composition as dispersion oremulsion, optionally together with high-boiling solvents, using suitabledispersing agents or emulsifiers. Suitable high boiling solvents aredescribed in Research Disclosure No. 37254 part VIII (1995) page 292.

The binders in the individual layers, and in particular gelatines, canalso be crosslinked by suitable compounds, so-called hardening agents,in order to improve the water and scratch resistance of the layers.Suitable hardening agents are described in Research Disclosure No. 37254part IX (1995) page 294, 37038 part XII (1995) page 86 and 38957 partIIB (1996) page 599 et seq. The hardening agents are normally used inquantities of 0.005 to 10% by weight, and preferably 0.01 to 1% byweight, based on the binder to be hardened.

The ink jet recording material can be produced in one pass from thesupport material and a casting solution for each layer to be applied, bymeans of a cascade or curtain casting device of the kind known from theproduction of photographic silver halide materials. After the castingsolution(s) has/have been cast on the support, the material is dried andis then ready for use. The individual layers have a dry layer thicknessof 0.1 to 20 μm, and preferably 0.5 to 5 μm.

The present sterically hindered amines can be dissolved either directlyin the ink or coating composition or added thereto in the form of anemulsion or suspension. As already mentioned, the present stericallyhindered amines can be also applied to the recording material in aseparate operation, alone or together with other already describedcomponents, as a solution in water or in a suitable organic solvent.Application can be made by spraying, by sizing in a sizing press, by aseparate coating operation or by immersion in a vat. After subjectingthe recording material to such an after treatment, an additional dryingstep is necessary.

The present photographic material can be a black and white or a colorphotographic material, color photographic material is preferred. Furtherdetails on the structure of color photographic material and thecomponents which can be employed in such materials are described in U.S.Pat. No. 5,538,840 at column 27, line 25 to column 106, line 16. Theserelevant parts are incorporated herein by reference. Application of theinstant novel compounds is essentially as described for UV absorbers orhindered amine stabilizers in U.S. Pat. No. 5,538,840.

Further important components, especially couplers, are described in U.S.Pat. No. 5,578,437.

Other articles which would benefit from the incorporation of theinstant, water compatible hindered amine compounds include laminatedarticles as described in U.S. Pat. Nos. 6,268,415 and 6,191,199, thedisclosures of which are hereby incorporated by reference. For example,laminated articles such as:

(a) Retroreflective Sheets and Signs and Conformable Marketing Sheets asseen in WO 97/42261; and U.S. Pat. No. 5,387,458 which is incorporatedherein by reference;

(b) Solar Control Films of Various Construction as seen in British2,012,668; European 355,962; and U.S. Pat. Nos. 3,290,203; 3,681,179;3,776,805 and 4,095,013 which are incorporated herein by reference;

(c) Corrosion Resistant Silver Mirrors and Solar Reflectors as seen inU.S. Pat. No. 4,645,714 which is incorporated herein by reference;

(d) Reflective Print Labels as seen in U.S. Pat. No. 5,564,843 which isincorporated herein by reference;

(e) UV Absorbing Glasses and Glass Coatings as seen in U.S. Pat. Nos.5,372,889; 5,426,204; 5,683,804 and 5,618,626 which are incorporatedherein by reference;

(f) Electrochromic Devices as seen in European 752,612 A1; and U.S. Pat.Nos. 5,239,406; 5,523,877 and 5,770,114 which are incorporated herein byreference;

(g) Films/Glazings as seen in WO 92/01557; Japanese Nos. 75-33286;93-143668; 95-3217 and 96-143831; and U.S. Pat. No. 5,643,676 which isincorporated herein by reference;

(h) Windscreens and Intermediate Layers as seen in Japanese Nos.80-40018; 90-192118; 90-335037; 90-335038; 92-110128 and 94-127591; and

(i) Optical Films as seen in WO 97/32225; and U.S. Pat. Nos. 4,871,784and 5,217,794 which are incorporated herein by reference.

As mentioned, the stabilized compositions of the invention mayoptionally also contain other conventional stabilizers. For example, thecompositions of this invention may contain from about 0.01 to about 5%,preferably from about 0.025 to about 2%, and especially from about 0.1to about 1% by weight of various conventional additives, such as thematerials listed below, or mixtures thereof.

1. Antioxidants

-   -   1.1. Alkylated monophenols, for example        2,6-di-tert-butyl-4-methylphenol,        2-tert-butyl-4,6-dimethylphenol,        2,6-di-tert-butyl-4-ethylphenol,        2,6-di-tert-butyl-4-n-butylphenol,        2,6-di-tert-butyl-4-isobutylphenol,        2,6-dicyclopentyl-4-methylphenol,        2-α-methylcyclohexyl)-4,6-dimethylphenol,        2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,        2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are        linear or branched in the side chains, for example,        2,6-di-nonyl-4-methylphenol,        2,4-dimethyl-6-(1-methylundec-1-yl)phenol,        2,4-dimethyl-6-(1-methylheptadec-1-yl)phenol,        2,4-dimethyl-6-(1-methyltridec-1-yl)phenol and mixtures thereof.    -   1.2. Alkylthiomethylphenols, for example        2,4-dioctylthiomethyl-6-tert-butylphenol,        2,4-dioctylthiomethyl-6-methylphenol,        2,4-dioctylthiomethyl-6-ethyl phenol,        2,6-di-dodecylthiomethyl-4-nonylphenol.    -   1.3. Hydroquinones and alkylated hydroquinones, for example        2,6-di-tert-butyl-4-methoxyphenol,        2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone,        2,6-diphenyl-4-octadecyloxyphenol,        2,6-di-tert-butylhydroquinone,        2,5-di-tert-butyl-4-hydroxyanisole,        3,5-di-tert-butyl-4-hydroxyanisole,        3,5-di-tert-butyl-4-hydroxyphenyl stearate,        bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.    -   1.4. Tocopherols, for example α-tocopherol, β-tocopherol,        γ-tocopherol, δ-tocopherol and mixtures thereof (Vitamin E).    -   1.5. Hydroxylated thiodiphenyl ethers, for example 2,        2′-thiobis(6-tert-butyl-4-methylphenol),        2,2′-thiobis(4-octylphenol),        4,4′-thiobis(6-tert-butyl-3-methylphenol),        4,4′-thiobis(6-tert-butyl-2-methylphenol),        4,4′-thiobis-(3,6-di-sec-amylphenol),        4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.    -   1.6. Alkylidenebisphenols, for example 2,        2′-methylenebis(6-tert-butyl-4-methylphenol),        2,2′-methylenebis(6-tert-butyl-4-ethylphenol),        2,2′-methylenebis[4-methyl-6-α-methylcyclohexyl)phenol],        2,2′-methylenebis(4-methyl-6-cyclohexylphenol),        2,2′-methylenebis(6-nonyl-4-methylphenol),        2,2′-methylenebis(4,6-di-tert-butylphenol),        2,2′-ethylidenebis(4,6-di-tert-butylphenol),        2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),        2,2′-methylenebis[6-α-methylbenzyl)-4-nonylphenol],        2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],        4,4′-methylenebis(2,6-di-tert-butylphenol),        4,4′-methylenebis(6-tert-butyl-2-methylphenol),        1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,        2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,        1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,        1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,        ethylene glycol        bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate],        bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,        bis[2-(3′tert-butyl-2-hydroxy-5-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,        1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,        2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,        2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,        1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.    -   1.7. Benzyl compounds, for example        3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,        octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,        tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,        tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,        1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,        di-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,        3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl        ester, bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol        terephthalate,        1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,        1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,        3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl        ester and 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid        monoethyl ester, calcium-salt.    -   1.8. Hydroxybenzylated malonates, for example        dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,        di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,        di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,        bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.    -   1.9. Aromatic hydroxybenzyl compounds, for example 1,        3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,        1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,        2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.    -   1.10. Triazine compounds, for example        2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,        2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,        2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,        2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,        1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-benzyl)isocyanurate,        1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,        2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,        1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-hexahydro-1,3,5-triazine,        1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.    -   1.11. Benzylphosphonates, for example        dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,        diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,        dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,        dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate,        the calcium salt of the monoethyl ester of        3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.    -   1.12. Acylaminophenols, for example 4-hydroxy-lauric acid        anilide, 4-hydroxy-stearic acid anilide,        2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine        and octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.    -   1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic        acid with mono- or polyhydric alcohols, e.g. with methanol,        ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol,        1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl        glycol, thiodiethylene glycol, diethylene glycol, triethylene        glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate,        N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,        3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,        4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.    -   1.14. Esters of        β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with        mono- or polyhydric alcohols, e.g. with methanol, ethanol,        n-octanol, i-octanol, octadecanol, 1,6-hexane-diol,        1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl        glycol, thiodiethylene glycol, diethylene glycol, triethylene        glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate,        N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol,        3-thiapentadecanol, trimethylhexanediol, trimethyl-olpropane,        4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.    -   1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic        acid with mono- or polyhydric alcohols, e.g. with methanol,        ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,        ethylene glycol, 1,2-propanediol, neopentyl glycol,        thiodiethylene glycol, diethylene glycol, triethylene glycol,        pentaerythritol, tris(hydroxyethyl)isocyanurate,        N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,        3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,        4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.    -   1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid        with mono- or polyhydric alcohols, e.g. with methanol, ethanol,        octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene        glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene        glycol, diethylene glycol, triethylene glycol, pentaerythritol,        tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,        3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,        trimethylolpropane,        4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.    -   1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic        acid e.g.        N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,        N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,        N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,        N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide        (Naugard®XL-1 supplied by Uniroyal).    -   1.18. Ascorbic acid (vitamin C)    -   1.19. Aminic antioxidants, for example        N,N′-di-isopropyl-p-phenylenediamine,        N,N′-di-sec-butyl-p-phenylenediamine,        N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,        N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,        N,N′-bis(1-methylheptyl)-p-phenylenediamine,        N,N′-dicyclohexyl-p-phenylenediamine,        N,N′-diphenyl-p-phenylenediamine,        N,N′-bis(2-naphthyl)-p-phenylenediamine,        N-isopropyl-N′-phenyl-p-phenylenediamine,        N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,        N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,        N-cyclohexyl-N′-phenyl-p-phenylenediamine,        4-(p-toluenesulfamoyl)diphenylamine,        N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine,        diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine,        N-phenyl-1-naphthylamine,        N-(4-tert-octylphenyl)-1-naphthylamine,        N-phenyl-2-naphthylamine, octylated diphenylamine, for example        p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,        4-butyrylaminophenol, 4-nonanoylaminophenol,        4-dodecanoylaminophenol, 4-octadecanoylaminophenol,        bis(4-methoxyphenyl)amine,        2,6-di-tert-butyl-4-dimethylaminomethylphenol,        2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,        N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,        1,2-bis[(2-methylphenyl)amino]ethane,        1,2-bis(phenylamino)propane, (o-tolyl)biguanide,        bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octylated        N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated        tert-butyl/tert-octyl-diphenylamines, a mixture of mono- and        dialkylated nonyldiphenylamines, a mixture of mono- and        dialkylated dodecyldiphenylamines, a mixture of mono- and        dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono-        and dialkylated tert-butyldiphenylamines,        2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a        mixture of mono- and dialkylated        tert-butyl/tert-octylphenothiazines, a mixture of mono- and        dialkylated tert-octyl-phenothiazines, N-allylphenothiazin,        N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,        N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,        bis(2,2,6,6-tetramethylpiperid-4-yl)-sebacate,        2,2,6,6-tetramethylpiperidin-4-one,        2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorbers and light stabilizers

-   -   2.1. 2-(2-Hydroxyphenyl)-2H-benzotriazoles, for example known        commercial hydroxyphenyl-2H-benzotriazoles and benzotriazoles as        disclosed in, U.S. Pat. Nos. 3,004,896; 3,055,896; 3,072,585;        3,074,910; 3,189,615; 3,218,332; 3,230,194; 4,127,586;        4,226,763; 4,275,004; 4,278,589; 4,315,848; 4,347,180;        4,383,863; 4,675,352; 4,681,905, 4,853,471; 5,268,450;        5,278,314; 5,280,124; 5,319,091; 5,410,071; 5,436,349;        5,516,914; 5,554,760; 5,563,242; 5,574,166; 5,607,987, 5,977,219        and 6,166,218 such as        2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,        2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,        2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole,        2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole,        5-chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,        5-chloro-2-(3-t-butyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,        2-(3-sec-butyl-5-t-butyl-2-hydroxyphenyl)-2H-benzotriazole,        2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole,        2-(3,5-di-t-amyl-2-hydroxyphenyl)-2H-benzotriazole,        2-(3,5-bis-α-cumyl-2-hydroxyphenyl)-2H-benzotriazole,        2-(3-t-butyl-2-hydroxy-5-(2-(ω-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,        phenyl)-2H-benzotriazole,        2-(3-dodecyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,        2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonyl)ethylphenyl)-2H-benzotriazole,        dodecylated 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,        2-(3-t-butyl-2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,        2-(3-tert-butyl-5-(2-(2-ethylhexyloxy)-carbonylethyl)-2-hydroxyphenyl)-5-chloro-2H-benzotriazole,        2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,        2-(3-t-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-2H-benzotriazole,        2-(3-t-butyl-5-(2-(2-ethylhexyloxy)carbonylethyl)-2-hydroxyphenyl)-2H-benzotriazole,        2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl-2H-benzotriazole,        2,2′-methylene-bis(4-t-octyl-(6-2H-benzotriazol-2-yl)phenol),        2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,        2-(2-hydroxy-3-t-octyl-5-α-cumylphenyl)-2H-benzotriazole,        5-fluoro-2-(2-hydroxy-3,5-di-α-cumyl-phenyl)-2H-benzotriazole,        5-chloro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,        5-chloro-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,        2-(3-t-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenyl)-5-chloro-2H-benzotriazole,        5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,        5-trifluoromethyl-2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole,        5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-octylphenyl)-2H-benzotriazole,        methyl        3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyhydrocinnamate,        5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-t-octylphenyl)-2H-benzotriazole,        5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-t-butylphenyl)-2H-benzotriazole,        5-trifluoromethyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole,        5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,        5-butylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole        and        5-phenylsulfonyl-2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole.    -   2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy,        4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,        4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives.    -   2.3. Esters of substituted and unsubstituted benzoic acids, as        for example 4-tert-butylphenyl salicylate, phenyl salicylate,        octylphenyl salicylate, dibenzoyl resorcinol,        bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol,        2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate,        hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl        3,5-di-tert-butyl-4-hydroxybenzoate,        2-methyl-4,6-di-tert-butylphenyl        3,5-di-tert-butyl-4-hydroxybenzoate.    -   2.4. Acrylates and malonates, for example,        α-cyano-β,β-diphenylacrylic acid ethyl ester or isooctyl ester,        α-carbomethoxy-cinnamic acid methyl ester,        α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl        ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,        N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline, Sanduvor®        PR25, dimethyl p-methoxybenzylidenemalonate (CAS #7443-25-6),        and Sanduvor® PR31,        di-(1,2,2,6,6-pentamethylpiperidin-4-yl)p-methoxybenzylidenemalonate        (CAS #147783-69-5).    -   2.5. Nickel compounds, for example nickel complexes of        2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the        1:1 or 1:2 complex, with or without additional ligands such as        n-butylamine, triethanolamine or N-cyclohexyldiethanolamine,        nickel dibutyldithiocarbamate, nickel salts of the monoalkyl        esters, e.g. the methyl or ethyl ester, of        4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel        complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl        undecylketoxime, nickel complexes of        1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional        ligands.    -   2.6. Sterically hindered amine stabilizers, for example        4-hydroxy-2,2,6,6-tetramethylpiperidine,        1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,        1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,        bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,        bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,        bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,        bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,        bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate,        the condensate of        1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and        succinic acid, linear or cyclic condensates of        N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine        and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine,        tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,        tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,        1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),        4-benzoyl-2,2,6,6-tetramethylpiperidine,        4-stearyloxy-2,2,6,6-tetramethylpiperidine,        bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)        malonate,        3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,        bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,        bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear        or cyclic condensates of        N,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine        and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of        2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine        and 1,2-bis(3-amino-propylamino)ethane, the condensate of        2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine        and 1,2-bis-(3-aminopropylamino)ethane,        8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,        3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,        3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,        a mixture of 4-hexadecyloxy- and        4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation        product of        N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine        and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a        condensation product of 1,2-bis(3-aminopropylamino)ethane and        2,4,6-trichloro-1,3,5-triazine as well as        4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.        [136504-96-6]);        N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,        N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,        2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane,        a reaction product of        7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane        and epichlorohydrin,        1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,        N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,        diester of 4-methoxy-methylene-malonic acid with        1,2,2,6,6-pentamethyl-4-hydroxypiperidine,        poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,        reaction product of maleic acid anhydride-α-olefin-copolymer        with 2,2,6,6-tetramethyl-4-aminopiperidine or        1,2,2,6,6-pentamethyl-4-aminopiperidine.

The sterically hindered amine may also be one of the compounds describedin U.S. Pat. No. 5,980,783, the relevant parts of which are herebyincorporated by reference, that is compounds of component I-a), I-b),I-c), I-d), I-e), I-f), I-g), I-h), I-i), I-j), I-k) or I-l), inparticular the light stabilizer 1-a-1, 1-a-2, 1-b-1, 1-c-1, 1-c-2,1-d-1, 1-d-2, 1-d-3, 1-e-1, 1-f-1, 1-g-1, 1-g-2 or 1-k-1 listed oncolumns 64-72 of said U.S. Pat. No. 5,980,783.

The sterically hindered amine may also be one of the compounds describedin EP 782994, for example compounds as described in claims 10 or 38 orin Examples 1-12 or D-1 to D-5 therein.

-   -   2.7. Sterically hindered amines substituted on the N-atom by a        hydroxy-substituted alkoxy group, for example compounds such as        1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,        1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine,        the reaction product of        1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidine with a carbon        radical from t-amylalcohol,        1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine,        1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine,        bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,        bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)adipate,        bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)succinate,        bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)glutarate        and        2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethyl-amino)-s-triazine.    -   2.8. Oxamides, for example 4, 4′-dioctyloxyoxanilide,        2,2′-diethoxyoxanilide,        2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,        2,2′-didodecyloxy-5,5′-di-tert-butoxanilide,        2-ethoxy-2′-ethyloxanilide,        N,N′-bis(3-dimethylaminopropyl)oxamide,        2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with        2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and        p-methoxy-disubstituted oxanilides and mixtures of o- and        p-ethoxy-disubstituted oxanilides.    -   2.9. Tris-aryl-o-hydroxyphenyl-s-triazines, for example known        commercial tris-aryl-o-hydroxyphenyl-s-triazines and triazines        as disclosed in, WO 96/28431 and U.S. Pat. Nos. 3,843,371;        4,619,956; 4,740,542; 5,096,489; 5,106,891; 5,298,067;        5,300,414; 5,354,794; 5,461,151; 5,476,937; 5,489,503;        5,543,518; 5,556,973; 5,597,854; 5,681,955; 5,726,309;        5,736,597; 5,942,626; 5,959,008; 5,998,116; 6,013,704;        6,060,543; 6,187,919; 6,242,598 and 6,255,483, for example        4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-s-triazine,        Cyasorb® 1164, Cytec Corp,        4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine,        2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine,        2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,        2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine,        2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine,        2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)-phenyl]-6-(4-chlorophenyl)-s-triazine,        2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine,        2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine,        2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,        2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,        2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine,        2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine        (* denotes a mixture of octyloxy, nonyloxy and decyloxy groups),        methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)phenyl]-s-triazine},        methylene bridged dimer mixture bridged in the 3:5′, 5:5′ and        3:3′ positions in a 5:4:1 ratio,        2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxy-phenyl)-s-triazine,        2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-α-cumylphenyl)-s-triazine,        2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,        2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine,        mixture of        4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropoxy)-phenyl)-s-triazine        and        4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-tridecyloxy-2-hydroxypropoxy)-phenyl)-s-triazine,        Tinuvin® 400, Ciba Specialty Chemicals Corp.,        4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-s-triazine        and 4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites,tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,distearyl pentaerythritol diphosphite,tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylenediphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxaphosphepin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g][1,3,2]dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite.

Especially preferred are the following phosphites:

Tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite,

5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N-methyl-N-octadecylhydroxylamineand the N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example N-benzyl-α-phenylnitrone,N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone,N-lauryl-α-undecylnitrone, N-tetradecyl-α-tridcyinitrone,N-hexadecyl-α-pentadecylnitrone, N-octadecyl-α-heptadecylnitrone,N-hexadecyl-α-heptadecylnitrone, N-ocatadecyl-α-pentadecylnitrone,N-heptadecyl-α-heptadecylnitrone, N-octadecyl-α-hexadecylnitrone,N-methyl-α-heptadecylnitrone and the nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Amine oxides, for example amine oxide derivatives as disclosed inU.S. Pat. Nos. 5,844,029 and 5,880,191, didecyl methyl amine oxide,tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amineoxide.

8. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643;DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102or 3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, and3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

9. Thiosynergists, for example dilauryl thiodipropionate or distearylthiodipropionate.

10. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

11. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

12. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example, calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zincpyrocatecholate.

13. Nucleating agents, for example inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds such as ioniccopolymers (ionomers).

14. Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

15. Dispersing Agents, such as polyethylene oxide waxes or mineral oil.

16. Other additives, for example plasticizers, lubricants, emulsifiers,pigments, dyes, optical brighteners, rheology additives, catalysts,flow-control agents, slip agents, crosslinking agents, crosslinkingboosters, halogen scavengers, smoke inhibitors, flameproofing agents,antistatic agents, clarifiers such as substituted and unsubstitutedbisbenzylidene sorbitols, benzoxazinone UV absorbers such as2,2′-p-phenylene-bis(3,1-benzoxazin-4-one), Cyasorb® 3638 (CAS#18600-59-4), and blowing agents.

The sterically hindered alkoxyamines and hydroxy substitutedalkoxyamines of the present invention are prepared according to knownmethods, with the additional step of incorporating a water compatible orwater soluble side chain.

The preparation of sterically hindered alkoxyamine stabilizers, alsoknown as N-alkoxy hindered amines and NOR hindered amines or NORhindered amine light stabilizers or NOR HALS, is disclosed for examplein U.S. Pat. Nos. 5,004,770 and 5,096,950, the relevant disclosures ofwhich are hereby incorporated by reference.

The preparation of sterically hindered hydroxy substituted alkoxyaminestabilizers, also known as hindered hydroxyalkoxyamine stabilizers,N-hydroxyalkoxy hindered amines, or NORol HALS, is disclosed for examplein U.S. Pat. Nos. 6,271,377, 6,392,041 and 6,376,584, the relevantdisclosures of which are hereby incorporated by reference.

The following non-limiting examples further illustrate the presentinvention.

Test compounds:

when E is 2-hydroxycyclohexyloxy or 2-hydroxy-2-methylpropoxy,

R_(x) is selected from the group consisting of

—NH₂ ³⁰ CH₂CH₂OHCl⁻, —NHCH₂CH₂OH, —NH₃ ⁺⁻OAc, ═NOH, —NHCH(CH₃)COO⁻K⁺,—NHCH₂CH₂N(CH₃)₂ ⁺⁻OAc, —NHCH₂CH₂SO₃ ⁻K⁺, —NHCH(COO⁻K⁺)CH₂CH₂SCH₃,—NHCH₂COO⁻K⁺, —NHCOCH₂OH, —NHCOCH₂NHCOCH₃, —NHCH₂CH₂CH₂SO₃H, —OCH₂CH₂OH,—OCH(CH₃)COO⁻K⁺, —OCH₂CH₂N(CH₃)₂ ⁺⁻OAc, —OCH₂CH₂SO₃ ⁻K⁺,—OCH(COO⁻K⁺)CH₂CH₂SCH₃, —OCH₂COO⁻K⁺, —OCOCH₂OH, —OCOCH₂NHCOCH₃ and—OCH₂CH₂CH₂SO₃H,

when E is benzyloxy, methoxy, propoxy, hexyloxy, heptyloxy, octyloxy orcyclohexyloxy,

R_(x) is selected from the group consisting of

—NH₂ ⁺CH₂CH₂OHCl⁻, —NH₃ ⁺⁻OAc, ═NOH, —NHCH(CH₃)COO⁻K⁺, —NHCH₂CH₂N(CH₃)₂⁺⁻OAc, —NHCH₂CH₂SO₃ ⁻K⁺, —NHCH(COO⁻K⁺)CH₂CH₂SCH₃, —NHCH₂COO⁻K⁺,—OCH(CH₃)COO⁻K⁺, —OCH₂CH₂N(CH₃)₂ ⁺⁻OAc, —OCH₂CH₂SO₃ ⁻K⁺,—OCH(COO⁻K⁺)CH₂CH₂SCH₃ and —OCH₂COO⁻K⁺, and

where E and E′ are 2-hydroxycyclohexyloxy, 2-hydroxy-2-methylpropoxy,benzyloxy, methoxy, propoxy, hexyloxy, heptyloxy, octyloxy orcyclohexyloxy, and

where R₅ comprises repeating units selected from the group consisting of

—(OCH₂CH₂)—, —(OCH₂CH₂(CH₃))—, —(CH₂CHCOOH)—, —(CH₂C(CH₃)COOH)—,—(CH₂CHCOOCH₃)—, —(NHCH₂CH₂)—, —(CH₂CHOH)—, —(CH₂CHCONH₂)— and—(CH₂CH(NHCOH))—.

The following Examples more particularly point out the aspects of thepresent invention.

The Examples are as follows:

Compounds: Examples 1-18, 22, 37, 39, 43, 52-54, 57, 59-60, 62 and102-111.

Ink Jet Media: Examples 23, 29-36 and 38.

Solubility: Examples 44-47.

Shampoo Formulations Examples 48-49.

Mouthwash Formulations Examples 50-51.

Coatings: Examples 101, 112-115.

Inks: Examples 19-20 and 24.

Further Ink Jet Media: Examples 21, 25-28 and 40-42.

Further Compounds: Examples 55-56, 58 and 61.

Further Shampoo Formulations: Examples 63-69 and 72.

Body care products, household products, textile and fabrics: Examples70-71 and 73-76.

Polymer Formulations (compositions, fibers, plaques, combination withflame retardants, etc.): Examples 77-99, 120-125, 144-146, 149-167 and173-174.

Further Coatings: Examples 100, 116-119, 126-141 and 147-148.

Photographic Compositions: Examples 142-143.

Photocured Inks: Examples 168-169.

Photocured Coatings: Examples 170-172.

EXAMPLE 1

Example 39 (8.4 g, 0.035 mole), ethanolamine (3 g, 0.05 mole), andcatalyst (10% Pd on C, 2 g, Engelhard Corp.) are added to 10 mL ofisopropanol in 100 mL of ethanol. The reactor is pressured to 45 psigwith hydrogen while heating to 60 C. After a reaction time of two hours,the reactor is vented and catalyst is removed by filtration. The solventis distilled off and the crude product is crystallized from 50 mL ofethyl acetate. The title compound is obtained (5.23 g, 52% yield) asclear white plates with a melting point of 130-132 C whose structure isconsistent with HNMR.

EXAMPLE 2

Example 39 (3.36 g, 0.14 mole) and hydroxylamine hydrochloride (1.39 g,0.02 mole) are dissolved in a solution of 50 mL of water and 50 mL ofethanol. The solution is neutralized to pH=10 with 2N aqueous sodiumhydroxide solution. The solution is refluxed for 5 hours after which thesolvent is distilled off and the residue is crystallized from ethylacetate. After drying to constant weight, the title compound is obtained(3.11 g, 86% yield) as a white solid with a melting point of 131-134 Cwhose structure is consistent with HNMR.

EXAMPLE 3

Example 2 (2.44 g, 0.0094 mole) is added to 50 mL of absolute ethanol.Sodium spheres (4 g, 0.17 mole) are added portionwise over thirtyminutes after which the mixture is refluxed for one hour. The solutionis poured into 200 mL of water and extracted thrice with 100 mL ofmethylene chloride. The combined organic layer is washed twice with 25mL of water, dried over magnesium sulfate, and the solvent is distilledoff. The title compound is obtained (2.3 g, 100% yield) as a white solidwith a melting point of 110-114 C whose structure is consistent withHNMR.

EXAMPLE 4

Example 39 (5.28 g, 0.022 mole), beta-alanine ethylester hydrochloride(3.84 g, 0.025 mole), and catalyst (PtO₂, 1.0 g, Engelhard Corp.) areadded to 75 mL of absolute ethanol. The reactor is pressured up to 45psig with hydrogen while heating to 60 C. After four hours, the reactoris vented and the catalyst is removed by filtration. Sixty-five mL ofethanol was distilled yielding a precipitate in the remaining ethanol.After filtration, the precipitate is recrystallized from methanol. Thetitle compound is obtained as a white solid with a melting point of215-220 C whose structure is consistent with HNMR.

EXAMPLE 5

Example 39 (5.28 g, 0.022 mole), I-alanine (2.23 g, 0.025 mole),potassium hydroxide (1.4 g, 0.025 mole), and catalyst (PtO₂, 0.5 g,Engelhard Corp.) are added to 50 mL of absolute methanol. The reactor ispressured up to 45 psig with hydrogen while heating to 60 C. After fourhours, the reactor is vented and the catalyst is removed by filtration.The solvent is removed by distillation and the residue is dried invacuo, which crystallizes during drying. The title compound is obtained(7 g, 100% yield) as a white glassy solid with a melting point of 65-70C whose structure is consistent with HNMR.

EXAMPLE 6

Example 39 (5.28 g, 0.022 mole), N,N-ethylenediamine (2.2 g, 0.025mole), and catalyst (PtO₂, 0.5 g, Engelhard Corp.) are added to 75 mL ofabsolute methanol. The reactor is pressured up to 45 psig with hydrogenwhile heating to 60 C. After one hour, the reactor is vented and thecatalyst is removed by filtration. The solvent is removed bydistillation and the residue is dissolved in 10 mL of acetonitrile andtitrated with 1.5 g of glacial acetic acid. The solvent is removed bydistillation and the residue is dried overnight in a vacuum oven. Thetitle compound is obtained (7.69 g) as a white solid with a meltingpoint of 72-74 C whose structure is consistent with HNMR.

EXAMPLE 7

Example 3 (2.55 g, 0.01 mole) is dissolved in 100 mL of diethylether. Tothis solution is added 0.56 g of glacial acetic acid. A solid, whichforms immediately, is filtered off, washed with diethylether, and driedto constant weight in a vacuum oven. The title compound is obtained (1.7g, 56% yield) as a white solid with a melting point of 200-202 C whosestructure is consistent with HNMR.

EXAMPLE 8

Example 39 (5.28 g, 0.022 mole), taurine (3.12 g, 0.025 mole), andcatalyst (PtO₂, 0.5 g, Engelhard Corp.) are added to 50 mL of methanoland 25 mL of 1 M methanolic potassium hydroxide. The reactor ispressured to 45 psig with hydrogen while heating to 60 C. After 4 hours,the reactor is vented and the catalyst is filtered off. The filtrate issubjected to vacuum distillation yielding a clear residue thatsolidifies upon standing. The title compound is obtained (7.7 g, 89.5%yield) as a glassy white solid with a melting point of 158-162 C whosestructure is consistent with HNMR.

EXAMPLE 9

Example 39 (5.28 g, 0.022 mole), methionine (3.72 g, 0.025 mole), andcatalyst (PtO₂, 0.5 g, Engelhard Corp.) are added to 50 mL of methanoland 25 mL of 1 M methanolic potassium hydroxide. The reactor ispressured to 45 psig with hydrogen while heating to 60 C. After 3 hours,the reactor is vented and the catalyst is filtered off. The filtrate issubjected to vacuum distillation yielding a clear residue thatsolidifies upon standing. The title compound is obtained (9.45 g) as awhite solid with a melting point of 108-112 C whose structure isconsistent with HNMR.

EXAMPLE 10

Example 39 (5.28 g, 0.022 mole), glycine (1.88 g, 0.025 mole), andcatalyst (PtO₂, 0.5 g, Engelhard Corp.) are added to 50 mL of methanoland 25 mL of 1 M methanolic potassium hydroxide. The reactor ispressured to 45 psig with hydrogen while heating to 60 C. After 2 hours,the reactor is vented and the catalyst is filtered off. The filtrate issubjected to vacuum distillation yielding a clear residue thatsolidifies upon standing. The title compound is obtained (7.87 g) as awhite solid with a melting point of 94-98 C whose structure isconsistent with HNMR.

EXAMPLE 11

Example 3 (6.11 g, 0.025 mole) and methyl glycolate (4.5 g, 0.05 mole)are added to 75 mL of xylene. Under a nitrogen atmosphere, the solutionis heated to 120 C. and held there for 18 hours. The solvent is removedby distillation and the residue is chromatographed on silica gel using ahexane:ethyl acetate gradient. The appropriate fractions are combinedand the solvent is removed by distillation yielding a clear residue thatsolidifies upon standing. The title compound is obtained (1.51 g, 20%yield) as a white solid with a melting point of 153-154 C whosestructure is consistent with HNMR.

EXAMPLE 12

Synthetic Reference: I. Ismail, J. Serb. Chem. Soc. 57(7), 415-420(1992)

Example 3 (4.88 g, 0.02 mole) and 1,1-propanesultone (2.44 g, 0.02 mole)are added to 60 mL of 2-butanol. Under a nitrogen atmosphere, thesolution is heated to reflux for 30 minutes. The precipitate is filteredat ambient temperature, washed with 2-butanol, and dried to constantweight in a vacuum oven. The title compound is obtained (4.45 g, 60.5%yield) as a white solid that decomposes upon melting at 290 C. whosestructure is consistent with HNMR.

EXAMPLE 13

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine(4.9 g, 0.02 mole) is dissolved in 200 mL of 1,2-dichloroethane andcooled to 5 C. To this solution is added drop wise chlorosulfonic acid(1.32 mL, 0.02 mole) dissolved in 25 mL of 1,2-dichloroethane. Thesolution is left stirring overnight allowing the temperature to rise toambient temperature. The solvent is removed by distillation and replacedwith ethanol. The solution is clarified and the ethanol is removed bydistillation. The title compound is obtained as a viscous clear resinwhose structure is consistent with HNMR.

Analysis:

HNMR (CD₃OD): δ 1.29 (s, 6H), 1.56 (s, 6H), 1.57 (s, 6H), 1.82 (dd, 2H),2.16 (ddd, 2H), 4.16 (tt, 1H), 4.17 (s, 2H)

EXAMPLE 14

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine(12.25 g, 0.05 mole), methyl glycolate (6.75 g, 0.075 mole), and TyzorTBT (0.5 mL, 0.0013 mole) are dissolved in 250 mL of dry toluene. Thesolution is heated to reflux and allowed to reflux for 5 hours. Thesolution is cooled to 100 C at which time 5 mL of water is added. Thewater is removed, the toluene layer is clarified, and the toluene isremoved by distillation. The title compound is obtained (17.56 g) as alight orange oil with an assay of 87% as judged by gas chromatographywhose structure is consistent with HNMR.

EXAMPLE 15

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine(12.25 g, 0.05 mole), ethylacetoacetate (7.65 mL, 0.06 mole), andlithium t-butoxide (0.5 g, 0.006 mole) are dissolved in 250 mL of drytoluene. The solution is heated to reflux using a Dean Stark trap andallowed to reflux for 6 hours. The solution is cooled to 100 C. at whichtime 5 mL of water is added to destroy the catalyst. The water isremoved, the toluene layer is clarified, and the toluene is removed bydistillation. The title compound is obtained (16.7 g) as a light orangeoil whose structure is consistent with HNMR.

EXAMPLE 16

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine(12.25 g, 0.05 mole), N,N-dimethylglycine ethyl ester (13 mL, 0.09mole), and lithium t-butoxide (0.2 g, 0.0025 mole) are dissolved in 150mL of dry toluene. The solution is heated to reflux using a Dean Starktrap and allowed to reflux for 5 hours. The solution is cooled to 100 C.at which time 5 mL of water is added to destroy the catalyst. The wateris removed, the toluene layer is clarified, and the toluene is removedby distillation. The title compound is obtained (15.58 g, 94% yield) asa light yellow-orange oil with an assay of 93.2% as judged by gaschromatography whose structure is consistent with HNMR.

EXAMPLE 17

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine(12.25 g, 0.05 mole), succinic acid monomethylester (6.6 g, 0.05 mole),triethylamine (5.05 g, 0.05 mole), and lithium t-butoxide (0.4 g, 0.005mole) are dissolved in 200 mL of dry toluene. The solution is heated toreflux using a Dean Stark trap and allowed to reflux for 8 hours. Thesolution is cooled to 100 C. at which time 5 mL of water is added todestroy the catalyst. The water is removed, the toluene layer isclarified, and the toluene is removed by distillation. The titlecompound is obtained as a light yellow-orange oil (21.9 g) with an assayof 21% (remaining material is unreacted starting hindered amine) asjudged by gas chromatography whose structure is consistent with HNMR.

EXAMPLE 18

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine(12.25 g, 0.05 mole), methyl 4-hydroxyisobutyrate (7.08 g, 0.06 mole),and titanium isopropoxide (0.75 mL, 0.0025 mole) are dissolved in 250 mLof dry toluene. The solution is heated to reflux using a Dean Stark trapand allowed to reflux for 18 hours. The solution is cooled to 100 C. atwhich time 5 mL of water is added to destroy the catalyst. The water isremoved, the toluene layer is clarified, and the toluene is removed bydistillation. The title compound is obtained (21.41 g) as a light-yellowoil with an assay of 79% as judged by gas chromatography whose structureis consistent with HNMR.

EXAMPLE 19 Ink Jet Ink

An ink-jet ink is prepared by dissolving 2 g of dye in 20 g ofdiethylene glycol and 78 g of deionized water. The dye used is Acid red52. The stabilizer is weighed in an amount of 0.15 g into a test tubeand dissolved in 2.85 g of ink. The obtained ink is filtered andtransferred into an emptied and carefully cleaned cartridge of a Deskjet510 printer (Hewlett-Packard). A stepped image is then printed ontoplain paper (sihl+eika). The produced print is left to dry at 50° C.under vacuum for two hours and thereafter irradiated behind a 5 mm thickwindow glass in an Atlas Ci-35 light fading device equipped with a Xenonlamp. The Atlas device is operated at 43° C., 50% RH without dark cyclesand the light intensity is 461 W/m² (300-800 nm). The color density ofeach step is measured before and after exposure using a MacBeth TR 924densitometer. The compounds according to this invention are able toimprove substantially the light fastness of the ink-jet print.

EXAMPLE 20

Magenta and Yellow inks are extracted from an Hewlett-Packardthree-color cartridge (HP C1823D). The stabilizer is weighed in anamount of 0.15 g into a test tube and dissolved in 2.85 g of either themagenta or yellow ink. The obtained ink is filtered and transferred intoan emptied and carefully cleaned cartridge of a Deskjet 510 printer(Hewlett-Packard). A stepped image is then printed onto plain paper(sihl+eika) or, alternatively, onto Premium Photo paper fromHewlett-Packard (item code C6040A). The produced print is left to dry at50° C. under vacuum for two hours and thereafter irradiated behind a 5mm thick window glass in an Atlas Ci-35 light fading device equippedwith a Xenon lamp. The Atlas device is operated at 43° C., 50% RHwithout dark cycles and the light intensity is 461 W/m² (300-800 nm).The color density of each step is measured before and after exposureusing a MacBeth TR 924 densitometer. The compounds according to thisinvention are able to improve the light fastness of the magenta andyellow prints.

EXAMPLE 21 Ink Jet Media

Canon PR-101 sheets (Canon Japan) are post-treated by casting stabilizersolutions, either aqueous or methanol, using a 75 micron wire woundcoating bar. After drying at room temperature, the thus modified sheetsare printed with cyan step images using a Canon BJC 8200 printer. Thecyan dye used is C.I. Direct Blue 199. The obtained prints are left todry at 50 C under vacuum for two hours and thereafter are subjected toforced airflow during four weeks. The color density is measured beforeand after exposure using a MacBeth TR 924 densitometer. The compoundsaccording to this invention are able to improve the light fastness ofdyes when printed onto printing media.

EXAMPLE 22

Example 1 (12.02 g as crude product, 0.042 mole) is dissolved in amixture of diethylether and ethanol. With vigorous agitation,hydrochloric acid gas is introduced subsurface to the solution. A whiteinsoluble solid is formed which is filtered off and dried in a vacuumoven until constant weight is reached. The title compound is obtained(2.16 g, 16% yield) as a white solid with a melting point of 217-233 Cwhose structure is consistent with HNMR.

EXAMPLE 23 Ink Jet Media

A resin-coated paper impregnated with inorganic adsorbent particles(Konica QP Photoglossy ink jet paper, Konica Corp.) is purchased. On theink-receiving layer, a 0.8 wt % methanol solution, unless statedotherwise, of the instant compounds is applied in an amount to achieve650-700 mg/m². The paper is allowed to dry under ambient temperature andpressure for 24 hours. Separately, test patterns (cyan) are printed onthe treated sheets using a Hewlett Packard DeskJet 970 Cxi printer at100% print density. The obtained prints are left to dry at ambienttemperature and pressure for 24 hours. Color densities and CIEL*a*bcoordinates before and after exposure are measured using X-Rite 938Spectrodensitometer. Exposures are carried out using normal officefluorescent lighting. The change in color is given by Delta E (DE) whichis calculated by:DE=[(DL*)²+(Da*)²+(Db*)²]^(1/2)

Stabilizer DE for cyan after 15 weeks None 4.29 Example 11/DABCO•HCl4.08 Example 6/DABCO 3.09 DABCO•HCl is 1,4-diazabicyclo[2.2.2]octanehydrochloride salt. DABCO is 1,4-diazabicyclo[2.2.2]octane. Mixtures ofstabilizers are in a 1:1 by weight ratio with the total stabilizerconcentration added of 650-700 mg/m2.

As the above data show, compounds according to this invention improvethe light fastness of ink jet prints.

EXAMPLE 24

The instant compounds are added to an ink composition, for example asdisclosed in U.S. Pat. No. 5,855,655 or 5,782,963, at a concentration of2 wt % and 0.5 wt % respectively. The images printed from thesestabilized inks show reduced dye fading and better image permanence.

EXAMPLE 25

A commercial white polyethylene terephthalate sheet is coated withsilica and polyvinylalcohol according to U.S. Pat. No. 6,391,440Example 1. A methanol solution of the instant compounds is applied tothis sheet in an amount equivalent to 400 mg/m². The image printed onthis receiving layer shows reduced dye fading and better imagepermanence.

EXAMPLE 26

A commercial white polyethylene terephthalate sheet is coated withalumina hydrate and polyvinylalcohol according to U.S. Pat. No.6,391,440 Example 5. A methanol solution of the instant compounds isapplied to this sheet in an amount equivalent to 400 mg/m². The imageprinted on this receiving layer shows reduced dye fading and betterimage permanence.

EXAMPLE 27

A paper sheet containing alumina is prepared according to U.S. Pat. No.6,391,440 Example 8. A methanol solution of the instant compounds isapplied to this sheet in an amount equivalent to 600 mg/m2. The imageprinted on this receiving layer shows reduced dye fading and betterimage permanence.

EXAMPLE 28

A paper sheet containing silica is prepared according to U.S. Pat. No.5,165,973. A methanol solution of the instant compounds is applied tothis sheet in an amount equivalent to 700 mg/m2. The image printed onthis receiving layer shows reduced dye fading and better imagepermanence.

EXAMPLE 29

A resin-coated paper impregnated with inorganic adsorbent particles(Konica QP Photoglossy ink jet paper, Konica Corp.) is purchased. On theink-receiving layer, a 0.8 wt % methanol solution of the instantcompounds is applied in an amount to achieve 650-700 mg/m². The paper isallowed to dry under ambient temperature and pressure for 24 hours.Separately, test patterns (magenta) are printed on the treated sheetsusing a Hewlett Packard DeskJet 970 Cxi printer at 100% print density.The obtained prints are left to dry at ambient temperature and pressurefor 24 hours. Color densities and CIEL*a*b coordinates before and afterexposure are measured using X-Rite 938 Spectrodensitometer. Exposuresare carried out using normal office fluorescent lighting.

Stabilizer DE for magenta after 15 weeks None 5.49 Example 11/DABCO•HCl4.79 Example 6/DABCO 2.23 DABCO•HCl is 1,4-diazabicyclo[2.2.2]octanehydrochloride salt. DABCO is 1,4-diazabicyclo[2.2.2]octane. Mixtures ofstabilizers are in a 1:1 by weight ratio with the total stabilizerconcentration added of 650-700 mg/m2.

As the above data show, compounds according to this invention improvethe light fastness of ink jet prints.

EXAMPLE 30

A resin-coated paper impregnated with inorganic adsorbent particles(Konica QP Photoglossy ink jet paper, Konica Corp.) is purchased. On theink-receiving layer, a 0.8 wt % methanol solution of the instantcompounds is applied in an amount to achieve 650-700 mg/m². The paper isallowed to dry under ambient temperature and pressure for 24 hours.Separately, test patterns (yellow) are printed on the treated sheetsusing a Hewlett Packard DeskJet 970 Cxi printer at 100% print density.The obtained prints are left to dry at ambient temperature and pressurefor 24 hours. Color densities and CIEL*a*b coordinates before and afterexposure are measured using X-Rite 938 Spectrodensitometer. Exposuresare carried out using normal office fluorescent lighting.

Stabilizer DE for yellow after 15 weeks None 2.48 Example 11/DABCO•HCl2.35 Example 6/DABCO 1.73 DABCO•HCl is 1,4-diazabicyclo[2.2.2]octanehydrochloride salt. DABCO is 1,4-diazabicyclo[2.2.2]octane. Mixtures ofstabilizers are in a 1:1 by weight ratio with the total stabilizerconcentration added of 650-700 mg/m2.

As the above data show, compounds according to this invention improvethe light fastness of ink jet prints.

EXAMPLE 31

A resin-coated paper impregnated with inorganic adsorbent particles(Konica QP Photoglossy ink jet paper, Konica Corp.) is purchased. On theink-receiving layer, a 0.8 wt % methanol solution of the instantcompounds is applied in an amount to achieve 650-700 mg/m², unlessotherwise stated. The paper is allowed to dry under ambient temperatureand pressure for 24 hours. Separately, test patterns (cyan) are printedon the treated sheets using a Hewlett Packard DeskJet 970 Cxi printer at100% print density. The obtained prints are left to dry at ambienttemperature and pressure for 24 hours. Color densities and CIEL*a*bcoordinates before and after exposure are measured using X-Rite 938Spectrodensitometer. Exposures are carried out using normal officefluorescent lighting.

Stabillizer DE for cyan after 4 weeks None 6.19 Example 22 5.26 Example2 4.69 Example 22 (2x) 4.62 Example 7 4.27 Example 1 4.21 Example 22(2x) is done at a concentration of 1300 to 1400 mg/m2.

As the above data show, compounds according to this invention improvethe light fastness of ink jet prints.

EXAMPLE 32

A resin-coated paper impregnated with inorganic adsorbent particles(Konica QP Photoglossy ink jet paper, Konica Corp.) is purchased. On theink-receiving layer, a 0.8 wt % methanol solution of the instantcompounds is applied in an amount to achieve 650-700 mg/m², unlessotherwise stated. The paper is allowed to dry under ambient temperatureand pressure for 24 hours. Separately, test patterns (magenta) areprinted on the treated sheets using a Hewlett Packard DeskJet 970 Cxiprinter at 100% print density. The obtained prints are left to dry atambient temperature and pressure for 24 hours. Color densities andCIEL*a*b coordinates before and after exposure are measured using X-Rite938 Spectrodensitometer. Exposures are carried out using normal officefluorescent lighting.

Stabilizer DE for magenta after 4 weeks None 25.73 Example 22 25.20Example 22 (2x) 21.96 Example 7 20.78 Example 1 20.23 Example 7 (2x)19.52 Example 7 (3x) 12.99 Example 22 (2x) and Example 7 (2x) are doneat a concentration of 1300 to 1400 mg/m2 while Example 7 (3x) is done ata concentration of 1950 to 2100 mg/m2.

As the above data show, compounds according to this invention improvethe light fastness of ink jet prints.

EXAMPLE 33

A resin-coated paper impregnated with inorganic adsorbent particles(Konica QP Photoglossy ink jet paper, Konica Corp.) is purchased. On theink-receiving layer, a 0.8 wt % methanol solution of the instantcompounds is applied in an amount to achieve 650-700 mg/m², unlessstated otherwise. The paper is allowed to dry under ambient temperatureand pressure for 24 hours. Separately, test patterns (yellow) areprinted on the treated sheets using a Hewlett Packard DeskJet 970 Cxiprinter at 50% print density. The obtained prints are left to dry atambient temperature and pressure for 24 hours. Color densities andCIEL*a*b coordinates before and after exposure are measured using X-Rite938 Spectrodensitometer. Exposures are carried out using normal officefluorescent lighting.

Stabilizer DE for yellow after 4 weeks None 5.80 Example 22 5.53 Example2 3.87

As the above data show, compounds according to this invention improvethe light fastness of ink jet prints.

EXAMPLE 34

A resin-coated paper impregnated with inorganic adsorbent particles(Konica QP Photoglossy ink jet paper, Konica Corp.) is purchased. On theink-receiving layer, a 0.8 wt % methanol solution of the instantcompounds is applied in an amount to achieve 650-700 mg/m², unlessotherwise stated. The paper is allowed to dry under ambient temperatureand pressure for 24 hours. Separately, test patterns (cyan) are printedon the treated sheets using a Hewlett Packard DeskJet 970 Cxi printer at50% print density. The obtained prints are left to dry at ambienttemperature and pressure for 24 hours. Color densities and CIEL*a*bcoordinates before and after exposure are measured using X-Rite 938Spectrodensitometer. Exposures are carried out using normal officefluorescent lighting.

Stabilizer DE for cyan after 4 weeks None 7.29 Example 22 5.98 Example 75.85 Example 2 5.53 Example 1 5.29 Example 22 (2x) 5.11 Example 7 (2x)4.95 Example 7 (3x) 4.34 Example 22 (2x) and Example 7 (2x) are done ata concentration of 1300 to 1400 mg/m2 while Example 7 (3x) is done at aconcentration of 1950 to 2100 mg/m2.

As the above data show, compounds according to this invention improvethe light fastness of ink jet prints.

EXAMPLE 35

A resin-coated paper impregnated with inorganic adsorbent particles(Konica QP Photoglossy ink jet paper, Konica Corp.) is purchased. On theink-receiving layer, a 0.8 wt % methanol solution of the instantcompounds is applied in an amount to achieve 650-700 mg/m², unlessotherwise stated. The paper is allowed to dry under ambient temperatureand pressure for 24 hours. Separately, test patterns (magenta) areprinted on the treated sheets using a Hewlett Packard DeskJet 970 Cxiprinter at 50% print density. The obtained prints are left to dry atambient temperature and pressure for 24 hours. Color densities andCIEL*a*b coordinates before and after exposure are measured using X-Rite938 Spectrodensitometer. Exposures are carried out using normal officefluorescent lighting.

Stabilizer DE for magenta after 4 weeks None 20.16 Example 7 16.62Example 7 (2x) 14.14 Example 7 (3x) 8.60 Example 7 (2x) is done at aconcentration of 1300 to 1400 mg/m2 while Example 7 (3x) is done at aconcentration of 1950 to 2100 mg/m2.

As the above data show, compounds according to this invention improvethe light fastness of ink jet prints.

EXAMPLE 36

A resin-coated paper impregnated with inorganic adsorbent particles(Konica QP Photoglossy ink jet paper, Konica Corp.) is purchased. On theink-receiving layer, a 0.8 wt % methanol solution of the instantcompounds is applied in an amount to achieve 650-700 mg/m², unlessstated otherwise. The paper is allowed to dry under ambient temperatureand pressure for 24 hours. Separately, test patterns (yellow) areprinted on the treated sheets using a Hewlett Packard DeskJet 970 Cxiprinter at 50% print density. The obtained prints are left to dry atambient temperature and pressure for 24 hours. Color densities andCIEL*a*b coordinates before and after exposure are measured using X-Rite938 Spectrodensitometer. Exposures are carried out using normal officefluorescent lighting.

Stabilizer DE for yellow after 4 weeks None 4.68 Example 22 3.15 Example2 1.36

As the above data show, compounds according to this invention improvethe light fastness of ink jet prints.

EXAMPLE 37

Example 3 (6.1 g, 0.025 mole) and ethyl acetamidoacetate (3.62 g, 0.025mole) are added to 75 mL of xylene and heated to reflux. The solution isrefluxed for 18 hours and then the xylene is removed by distillation.The remaining orange residue is recrystallized from methylene chlorideand dried to constant weight in a vacuum oven. The title compound isobtained (2.41 g, 28% yield) as a white crystalline solid with a meltingpoint of 77-80 C whose structure is consistent with HNMR.

EXAMPLE 38

A resin-coated paper impregnated with inorganic adsorbent particles(Konica QP Photoglossy ink jet paper, Konica Corp.) is purchased. On theink-receiving layer, a 0.8 wt % methanol solution of the instantcompounds is applied in an amount to achieve 650-700 mg/m². The paper isallowed to dry under ambient temperature and pressure for 24 hours.Separately, test patterns (cyan and yellow) are printed on the treatedsheets using a Hewlett Packard DeskJet 970 Cxi printer at 100% printdensity. The obtained prints are left to dry at ambient temperature andpressure for 24 hours. Color densities and CIEL*a*b coordinates beforeand after exposure are measured using X-Rite 938 Spectrodensitometer.Exposures are carried out using normal office fluorescent lighting.

Stabilizer DE for cyan after 3 months None 12.40 Compound A 11.96Example 37 11.39 Compound A/Example 37 10.96Compound A is N,N-dibenzylhydroxylamine hydrochlorideMixtures of stabilizers are in a 1:1 by weight ratio with the totalstabilizer concentration added of 650-700 mg/m2.

Stabilizer DE for yellow after 3 months None 6.85 Compound A 5.31Example 37 2.96 Example 37/Compound A 1.37Compound A is N,N-dibenzylhydroxylamine hydrochlorideMixtures of stabilizers are in a 1:1 by weight ratio with the totalstabilizer concentration added of 650-700 mg/m2.

As the above data show, compounds according to this invention improvethe light fastness of ink jet prints.

EXAMPLE 39

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine(42.5 g, 0.17 mole), calcium hypochlorite (100 g, 0.7 mole), and resin(25 g, IRA 900 resin, ACROS) are added to 600 mL of carbontetrachloride. After heating to 40 C, the slurry is stirred for sevenhours and then is stirred overnight at ambient temperature. The slurryis filtered to remove resin and salts. The resulting filtrate is washedtwice with water, dried over magnesium sulfate and the solvent removedby distillation. The title compound is obtained (37.1 g, 88% yield) as awhite solid with a melting point of 58-61 C whose structure isconsistent with HNMR.

EXAMPLE 40 Ink Jet Media

A resin-coated paper impregnated with inorganic adsorbent particles(Konica QP Photoglossy ink jet paper, Konica Corp.) is purchased. On theink-receiving layer, a 0.8 wt % methanol solution of the instantcompounds and2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole-5-sulfonicacid, sodium salt, a benzotriazole based UV absorber, is applied in anamount to achieve 650-700 mg/m². The UV absorber and the instantcompounds are in a 2:1 ratio by weight. The paper is allowed to dryunder ambient temperature and pressure for 24 hours. Separately, testpatterns (cyan, magenta and yellow) are printed on the treated sheetsusing an Epson printer at 100% print density. The obtained prints areleft to dry at ambient temperature and pressure for 24 hours. Colordensities and CIEL*a*b coordinates before and after exposure aremeasured using X-Rite 938 Spectrodensitometer. Exposures are carried outusing normal office fluorescent lighting. The compounds according tothis invention improve the light fastness of ink jet prints.

EXAMPLE 41

A resin-coated paper impregnated with inorganic adsorbent particles(Konica QP Photoglossy ink jet paper, Konica Corp.) is purchased. On theink-receiving layer, a 0.8 wt % methanol solution of the instantcompounds and2-(3-t-butyl-2-hydroxy-5-(2-(co-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,phenyl)-2H-benzotriazole, a benzotriazole based UV absorber, is appliedin an amount to achieve 650-700 mg/m². The UV absorber and the instantcompounds are in a 1:1 ratio by weight. The paper is allowed to dryunder ambient temperature and pressure for 24 hours. Separately, testpatterns (cyan, magenta and yellow) are printed on the treated sheetsusing a Hewlett Packard DeskJet 970 Cxi printer at 50% print density.The obtained prints are left to dry at ambient temperature and pressurefor 24 hours. Color densities and CIEL*a*b coordinates before and afterexposure are measured using X-Rite 938 Spectrodensitometer. Exposuresare carried out using uv lamps. The compounds according to thisinvention improve the light fastness of ink jet prints.

EXAMPLE 42

A resin-coated paper impregnated with inorganic adsorbent particles(Konica QP Photoglossy ink jet paper, Konica Corp.) is purchased. On theink-receiving layer, a 0.8 wt % methanol solution of the instantcompounds and2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole-5-sulfonicacid, sodium salt, a benzotriazole based UV absorber, is applied in anamount to achieve 650-700 mg/m². The UV absorber and the instantcompounds are in a 1:1 ratio by weight. The paper is allowed to dryunder ambient temperature and pressure for 24 hours. Separately, testpatterns (cyan, magenta and yellow) are printed on the treated sheetsusing a Hewlett Packard DeskJet 970 Cxi printer at 100% print density.The obtained prints are left to dry at ambient temperature and pressurefor 24 hours. Color densities and CIEL*a*b coordinates before and afterexposure are measured using X-Rite 938 Spectrodensitometer. Exposuresare carried out using normal office fluorescent lighting. The compoundsaccording to this invention improve the light fastness of ink jetprints.

EXAMPLE 43

Example 13 (0.304 g, 0.001 mole) is dissolved in 2 mL of absoluteethanol. Potassium hydroxide (0.05 g, 0.001 mole) is added to thesolution at which time a precipitate is formed. The precipitate isfiltered and dried to constant weight in a vacuum oven. The titlecompound is obtained as a waxy white solid with a melting point of115-120 C whose structure is consistent with HNMR.

EXAMPLE 44

The solubility of the instant compounds is evaluated in polar solventsystems. A solution of 50% butyl carbitol by weight and 50% water byweight is prepared. The instant compounds are added to this solution,stirred for 30 minutes, and sampled for analysis. Samples containingbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidineare filtered to remove any undissolved residue and all samples areanalyzed by high pressure liquid chromatography or gas chromatography.

Compound Solubility (% by weight) HALS A 0.2 HALS B 13.4 Example 5 ≧15Example 10 ≧20 HALS A isbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; HALS B is4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine.

This demonstrates that the instant compounds are soluble in highly polarsolvents.

EXAMPLE 45

The solubility of the instant compounds is evaluated in polar solventsystems. A solution of 50% butyl cellusolve by weight and 50% water byweight is prepared. The instant compounds are added to this solution,stirred for 30 minutes, and sampled for analysis. Samples containingbis(1-octyloxy-2,2,6,6-tetramethyl piperidin-4-yl)sebacate and4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidineare filtered to remove any undissolved residue and all samples areanalyzed by high pressure liquid chromatography or gas chromatography.

Compound Solubility (% by weight) HALS A 0.7 HALS B 15.5 Example 5 ≧18Example 10 ≧20 HALS A isbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; HALS B is4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine.

This demonstrates that the instant compounds are soluble in highly polarsolvents.

EXAMPLE 46

The solubility of the instant compounds is evaluated in polar solventsystems. A solution of 25% butyl cellusolve by weight and 75% water byweight is prepared. The instant compounds are added to this solution,stirred for 30 minutes, and sampled for analysis. Samples containingbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate and4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidineare filtered to remove any undissolved residue and all samples areanalyzed by high pressure liquid chromatography or gas chromatography.

Compound Solubility (% by weight) HALS A <0.1 HALS B 13.6 Example 10 ≧18HALS A is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.HALS B is4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine.

This demonstrates that the instant compounds are soluble in highly polarsolvents.

EXAMPLE 47

The solubility of the instant compounds is evaluated in polar solventsystems. The instant compounds are added to water, stirred for 30minutes, and sampled for analysis. Samples containingbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate and4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidineare filtered to remove any undissolved residue and all samples areanalyzed by high pressure liquid chromatography or gas chromatography.

Compound Solubility (% by weight) HALS A <0.1 HALS B 1.4 Example 10 ≧8HALS A is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate;HALS B is4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine.

This demonstrates that the instant compounds are soluble in highly polarsolvents.

EXAMPLE 48

The instant compounds are added to a commercial shampoo formulation andare evaluated for their ability to reduce the amount of dye fading whenthe samples are exposed to fluorescent lighting. The instant compounds(0.36 g) are dissolved in 5 mL of methanol which is then added to 120 gof shampoo (Suave® Natural®, Fresh Mountain Strawberry) with agitation.A benzotriazole UV absorber,2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole-5-sulfonicacid, sodium salt (UVA), is optionally added to the shampoo formulationat an equivalent concentration. The stabilized shampoo formulation isagitated for 15 minutes and put into 20 mL glass scintillation vials.These formulations are weathered under fluorescent light aging atambient temperature. The CIEL*a*b coordinates before and after exposureare measured using X-Rite 938 Spectrodensitometer. Color change isexpressed as Delta E (DE).

Stabilizer/(Loading) DE after 2 weeks None 11.74 Example 17/(0.30 wt %)8.91 Example 6/(0.30 wt %) 7.53 Example 6/UVA 2.33 (0.30 wt %/0.30 wt %)

The compounds according to this invention improve the light fastness ofshampoo formulations.

EXAMPLE 49

The instant compounds are added to a commercial shampoo formulation andare evaluated for their ability to reduce the amount of dye fading whenthe samples are exposed to fluorescent lighting. The instant compounds(0.36 g) are dissolved in 5 mL of methanol which is then added to 120 gof shampoo (Clairol® Herbal Essences Shampoo) with agitation. Abenzotriazole UV absorber,2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole-5-sulfonicacid, sodium salt (UVA), is optionally added to the shampoo formulation.The stabilized shampoo formulation is agitated for 15 minutes and putinto 20 mL glass scintillation vials. These formulations are weatheredunder fluorescent light aging at ambient temperature. The CIEL*a*bcoordinates before and after exposure are measured using X-Rite 938Spectrodensitometer. Color change is expressed as Delta E (DE).

Stabilizer/(Loading) DE after 2 weeks None 8.87 Example 7/(0.30 wt %)3.96 Example 5/(0.30 wt %) 1.55 Example 7/UVA 0.86 (0.15 wt %/0.15 wt %)

The compounds according to this invention improve the light fastness ofshampoo formulations.

EXAMPLE 50

The instant compounds are added to a commercial mouthwash formulationand are evaluated for their ability to reduce the amount of dye fadingwhen the samples are exposed to fluorescent lighting. The instantcompounds (0.36 g) are dissolved in 5 mL of methanol which is then addedto 120 g of mouthwash (Scope® Original Mint) with agitation. Abenzotriazole UV absorber,2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole-5-sulfonicacid, sodium salt (UVA), is optionally added to the mouthwashformulation. The stabilized mouthwash formulation is agitated for 15minutes and put into 20 mL glass scintillation vials. These formulationsare weathered under fluorescent light aging at ambient temperature. TheCIEL*a*b coordinates before and after exposure are measured using X-Rite938 Spectrodensitometer. Color change is expressed as Delta E (DE).

Stabilizer/(Loading) DE after 2 weeks None 6.15 Example 18/(0.30 wt %)5.11 Example 8/UVA 4.28 (0.15 wt %/0.15 wt %)

The compounds according to this invention improve the light fastness ofmouthwash formulations.

EXAMPLE 51

The instant compounds are added to a commercial mouthwash formulationand are evaluated for their ability to reduce the amount of dye fadingwhen the samples are exposed to fluorescent lighting. The instantcompounds (0.36 g) are dissolved in 5 mL of methanol which is then addedto 120 g of mouthwash (Listerine® Cool Mint) with agitation. Abenzotriazole UV absorber,2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole-5-sulfonicacid, sodium salt (UVA), is optionally added to the mouthwashformulation. The stabilized mouthwash formulation is agitated for 15minutes and put into 20 mL glass scintillation vials. These formulationsare weathered under fluorescent light aging at ambient temperature. TheCIEL*a*b coordinates before and after exposure are measured using X-Rite938 Spectrodensitometer. Color change is expressed as Delta E (DE).

Stabilizer/(Loading) DE after 35 days None 1.83 Example 10/UVA 1.21(0.15 wt %/0.15 wt %)

The compounds according to this invention improve the light fastness ofmouthwash formulations.

EXAMPLE 52

2,4-Bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-1,3,5-triazine(20 g, 27.8 mmol) is added to DMF (150 g) at 60° C. in a stirred vessel.N4 amine (50.3 g, 288 mmol, BASF) is quickly added and the reaction massis stirred at 60-65° C. for 1.5 hrs. Cyclohexane (150 mL) and water (200g) are then added and the reaction mass is stirred at 50-55° C. After 15minutes, the layers are allowed to separate. The aqueous layer is washedwith cyclohexane (70 mL) at 50° C. and the cyclohexane layers arecombined. The combined cyclohexane layer is washed thrice with water(100 mL/wash) at 50-55° C. The cyclohexane layer is briefly dried overanhydrous Na₂SO₄ before removing the solvent under reduced pressure. Thetitle compound is received (24.2 g) as a light yellow oil whosestructure is consistent with HNMR.

EXAMPLE 53

Example 52 (24.2 g, 27.8 mmol) is combined with cyclohexane (70 ml) andglacial acetic acid (1.68 g, 27.8 mmol). The solution is stirred 5minutes and the solvent stripped under reduced pressure until constantweight. The title compound is received (25 g) as an off white solidwhose structure is consistent with HNMR.

EXAMPLE 54

2,4-Bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-1,3,5-triazine(13.0 g, 0.0178 mole) and N,N-dimethylformamide (12.5 g, 1.71 mole) areadded to a 500 mL laboratory flask equipped with the necessary auxiliaryequipment. This solution is heated to 100 C. at which time sulfanilicacid (14.9 g, 0.0857 mole) and anhydrous potassium carbonate (11.0 g,0.0796 mole) are added. The temperature is raised to 145-150 C at whichtime sodium hydroxide (1.24 g, 0.031 mole) is added. After 15 hours at145-150 C, the reaction is cooled, diluted with water, and extractedwith hexane. The lower aqueous layer is removed and further washed withhexane. The combined hexane extracts is washed thrice with water at 50C. The organic solvent is removed and the product is dried untilconstant weight. The title compound is received (17.1 g) as a yellowglassy solid whose structure is consistent with HNMR.

EXAMPLE 55

Example 54 is dissolved in 2-propanol and heated to 50 C. The product istitrated with potassium hydroxide. The solvent is removed under vacuumand the resulting title compound is dried to constant weight.

EXAMPLE 56

Example 54 is dissolved in 2-propanol and heated to 50 C. The product istitrated with sodium hydroxide. The solvent is removed under vacuum andthe resulting title compound is dried to constant weight.

EXAMPLE 57

2,4-Bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-1,3,5-triazine(13.0 g, 0.0178 mole) and N,N-dimethylformamide (12.5 g, 1.71 mole) areadded to a 500 mL laboratory flask equipped with the necessary auxiliaryequipment. This solution is heated to 85 C at which time5-amino-2-chlorobenzoic acid (15 g, 0.0874 mole) and anhydrous potassiumcarbonate (11.0 g, 0.0796 mole) are added. The temperature is raisedslowly to 120 C and held at this temperature for 15 hours. The reactionis then diluted with water and extracted with hexane. The lower aqueouslayer is removed and further washed with hexane. The combined hexaneextracts is washed thrice with water at 50 C. The organic solvent isremoved and the product is dried until constant weight. The titlecompound is received (14.5 g) as a light yellow glassy solid.

EXAMPLE 58

Example 57 is dissolved in 2-propanol and heated to 50 C. The product istitrated with sodium hydroxide. The solvent is removed under vacuum andthe resulting title compound is dried to constant weight.

EXAMPLE 59

Example 54 (17.1 g, 0.0197 mole) is dissolved in anhydrous 2-propanol(150 g, 2.5 mole) and heated to 45 C. Dropwise addition of anhydrous HClgas (4.0 g, 0.11 mole) dissolved in 2-propanol (50 g, 0.83 mole) to thesolution is completed in an hour and held an additional 4 hours. Thesolvent is removed under vacuum and the resulting compound is dried toconstant weight. The title compound is received (18.6 g) as a yellowglassy solid whose structure is consistent with HNMR.

EXAMPLE 60

2,4-Bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-1,3,5-triazine(40 g, 54.6 mmol) is mixed with N,N-dimethylformamide (220 g) and heatedto 65° C. 1-(2-Aminoethyl)piperazine (14.5 g, 112.2 mmol) is then addedquickly and the reaction is stirred at 65° C. After 2 hrs, cyclohexane(150 g) and water (65 g) are added and the mixture stirred for 10minutes. The layers are allowed to separate and removed from thereactor. The bottom aqueous phase is returned to the pot, heated to 55°C. and water (112 g) is added. The aqueous layer is then washed twice at55° C. with cyclohexane (50 g/each). The cyclohexane layers are combinedand washed four times with water (30 g/each) at 55° C. The cyclohexanelayer is dried briefly over anhydrous Na₂SO₄ before removing the solventunder reduced pressure until a constant weight is received. The titlecompound is received (43.4 g) as a light yellow solid whose structure isconsistent with HNMR.

EXAMPLE 61

Example 60 is dissolved in 2-propanol. The product is then titrated withglacial acetic acid. The solvent is removed under vacuum and theresulting title compound is dried to constant weight.

EXAMPLE 62

Example 60 (43.4 g, 53 mmol) is dissolved in cyclohexane (80 g).Anhydrous HCl gas (2 g, 54.8 mmol) is dissolved in 2-propanol (12 g) andadded to the cyclohexane solution. The mixture is stirred for 10 minutesand the solvent then distilled under reduced pressure to a constantweight. The title compound is obtained (45 g) as a light yellow solidwhose structure is consistent with HNMR.

EXAMPLE 101

Formulation Reference: NeoResins, Inc., Formulation WB-2010, TechnicalBrochure, August, 2000

The following components are mixed together under good agitation:

Butyl cellusolve 5.68 parts Carbitol 4.26 parts Triton X-100 0.25 partsWater 1.66 parts Instant compound 0.58 parts

This solution is added to a 4 ounce clear glass jar containing 72.85parts of NeoPac R-9699 under vigorous agitation and agitated for 10minutes. Optionally, a defoamer, like Dehydran 1620 (Henkel), and aflash rusting agent, like Heiscore XAB (Cas Chem), are added. The lid isplaced securely on the jar. The solidified coatings are visuallyobserved for clarity after solidification. The development of opacity orhaziness is indicative of an incompatibility between the hindered aminestabilizer and the formulated coating.

Solidified Coating in Jar

Sample* 0 days 1 day 19 days A clear clear clear B hazy hazy hazy Cclear clear clear D clear clear clear E clear clear clear F clear clearclear G clear clear clear H clear clear clear I clear clear clear Jclear clear clear K clear clear clear L clear clear clear M clear clearclear N clear clear clear *A is unstabilized. B contains 2% by weight ofbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate. C contains2% by weight of Instant Example 17. D contains 2% by weight of InstantExample 7. E contains 2% by weight of Instant Example 12. F contains 2%by weight of Instant Example 8. G contains 2% by weight of instantExample 57. H contains 2% by weight of Instant Example 59. I contains 2%by weight of Instant Example 53. J contains 2% by weight of InstantExample 62. K contains 2% by weight of Instant Example 111. L contains2% by weight of Instant Example 107. M contains 2% by weight of InstantExample 105. N contains 2% by weight of Instant Example 109.

These data show that the instant compounds provide excellent solubilityand compatibility in a high solids water borne urethane/acryliccopolymer coating system.

EXAMPLE 102

2,2,6,6-Tetramethylpiperid-4-one (35 g, 0.2 mole) and Jeffamine D-400(38.2 g, 0.095 mole, Huntsman) are added to cyclehexane (300 mL). Thesolution is heated to reflux and refluxed for four hours whilecollecting the water by-product in a Dean-Stark trap. Xylene (300 mL) isadded and reflux is continued for four more hours. The solvent isremoved by vacuum distillation and the resulting product is dried toconstant weight. The title compound is received (69.2 g) as a viscousamber liquid whose structure is consistent with HNMR.

EXAMPLE 103

Example 102 (30 g, 0.044 mole) is dissolved in ethanol (250 mL). Sodiumborohydride (1.7 g, 0.044 mole) is added to the solution in one portionwith agitation. The resulting solution is stirred overnight at ambienttemperature. The solvent is removed by vacuum distillation and theresidue is redissolved in ethyl acetate. The solution is washedrepeatedly with water. The organic layer is then dried, the solventremoved by vacuum distillation, and the residue is dried to constantweight. The title compound is received (28 g) as a light yellow oilwhose structure is consistent with HNMR.

EXAMPLE 104

1-Methoxy-2,2,6,6-tetramethylpiperid-4-one (20 g, 0.108 mole) andJeffamine D-400 (22 g, 0.049 mole, Huntsman) are added to toluene (300mL). The solution is heated to reflux and refluxed for four hours whilecollecting the water by-product in a Dean-Stark trap. The solvent isremoved by vacuum distillation and the resulting product is dried toconstant weight. The title compound is received (41 g) as a light yellowliquid whose structure is consistent with HNMR.

EXAMPLE 105

Example 104 (30 g, 0.04 mole) is dissolved in ethanol (300 mL). Sodiumborohydride (1.5 g, 0.04 mole) is added to the solution in one portionwith agitation. The resulting solution is stirred overnight at ambienttemperature. The solvent is removed by vacuum distillation and theresidue is redissolved in ethyl acetate. The solution is washedrepeatedly with water. The organic layer is then dried, the solventremoved by vacuum distillation, and the residue is dried to constantweight. The title compound is received (26 g) as a light yellow oilwhose structure is consistent with HNMR.

This is an example of a compound of formula (7) where R₅ is ahomooligomer of propylene oxide.

EXAMPLE 106

Following the procedure described in Example 104,1-methoxy-2,2,6,6-tetramethylpiperid-4-one (25 g, 0.135 mole) andJeffamine XTJ-504 (9.9 g, 0.067 mole, Huntsman) are reacted together.The title compound is received (32.4 g) as a light yellow oil whosestructure is consistent with HNMR.

EXAMPLE 107

Following the synthetic procedure described in Example 105, Example 106(32.4 g) is reduced to yield the title compound (26 g) as a light yellowoil whose structure is consistent with HNMR.

EXAMPLE 108

Following the procedure described in Example 104,1-methoxy-2,2,6,6-tetramethylpiperid-4-one (6 g, 0.0324 mole) andJeffamine XTJ-500 (10 g, 0.0166 mole, Huntsman) are reacted together.The title compound is received (15.4 g) as a light yellow oil whosestructure is consistent with HNMR.

EXAMPLE 109

Following the synthetic procedure described in Example 105, Example 108(15.4 g) is reduced to yield the title compound (14 g) as a light yellowoil whose structure is consistent with HNMR.

This compound is an example of a compound of formula (7) where R₅ is aco-oligomer of ethylene oxide and propylene oxide.

EXAMPLE 110

Following the procedure described in Example 104,1-methoxy-2,2,6,6-tetramethylpiperid-4-one (25 g, 0.135 mole) andJeffamine XTJ-506 (128 g, 0.128 mole, Huntsman) are reacted together.The title compound is received (150.5 g) as a light yellow oil whosestructure is consistent with HNMR.

EXAMPLE 111

Following the synthetic procedure described in Example 105, Example 110(150.5 g) is reduced to yield the title compound (44.1 g) as a lightyellow oil whose structure is consistent with HNMR.

EXAMPLE 112

Formulation Reference: NeoResins, Inc., Formulation WB-2065, TechnicalBrochure.

The following components are mixed together under good agitation:

Water 31.2 parts Aqua Ammonia (26%)  1.3 parts

This solution is added to a 4 ounce clear glass jar containing 54.14parts of NeoCryl BT-520 and 0.43 parts of Instant Stabilizer undervigorous agitation and is agitated for 10 minutes. The lid is placedsecurely on the jar. The liquid coating samples are visually observedfor clarity over time. The development of opacity or haziness isindicative of an incompatibility between the hindered amine stabilizerand the formulated coating.

Liquid Coating in Jar

Sample* 0 Day 1 1 Month A clear clear clear B hazy hazy hazy C clearclear clear D clear clear clear E clear clear clear F clear clear clear*A is unstabilized B contains 2% by weight ofbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate C contains 2%by weight of Instant Example 111 D contains 2% by weight of InstantExample 107 E contains 2% by weight of Instant Example 105 F contains 2%by weight of Instant Example 109

These data show that the instant compounds provide excellent solubilityand compatibility in an alkali-soluble, water-borne acrylic copolymercoating system.

EXAMPLE 113

Formulation Reference: Bayer Corp., 2K Waterborne Clear, Notebook#820894-A, Technical Brochure.

The following components are mixed together under good agitation:

Bayhydrol VP LS 2235 51.66 parts  Deionized Water 15.70 parts  BorchigelLW 44 0.24 parts Instant Stabilizer 1.15 parts UVA 0.73 parts BaysilonePaint Additive VP AI 3468 0.28 parts UVA is2-(3-t-butyl-2-hydroxy-5-(2-(ω-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,phenyl)-2H-benzotriazole,a benzotriazole based UV absorber.

This solution is added to a 4 ounce clear glass jar containing 15.56parts of Bayhydur XP-7165 and 3.91 parts of Exxate 700 under vigorousagitation and is agitated for 10 minutes. The lid is placed securely onthe jar. The solidified coating samples are visually observed forclarity over time. The development of opacity or haziness is indicativeof an incompatibility between the hindered amine stabilizer and theformulated coating.

Solidified Coating in Jar

Sample* 0 Day 1 1 Month A clear clear clear B hazy hazy hazy C clearclear clear D clear clear clear E clear clear clear F clear clear clear*A is unstabilized B contains 2% by weight ofbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate C contains 2%by weight of Instant Example 111 D contains 2% by weight of InstantExample 107 E contains 2% by weight of Instant Example 105 F contains 2%by weight of Instant Example 109

These data show that the instant compounds provide excellent solubilityand compatibility in a two component, water-borne polyurethane coatingsystem.

EXAMPLE 114

The hindered amine test stabilizers are incorporated into a coatingsystem as described in Example 112. A 9.5-10 gram sample of each of theliquid coatings is added to a 100 mm×15 mm Petri dish and is placed inan oven at 65 C for thirty minutes. The samples are taken out of theoven, allowed to cool, and are visually observed for clarity over time.The development of opacity or haziness is indicative of anincompatibility between the hindered amine stabilizer and the formulatedcoating.

Solidified Coating in Petri Dish

Sample* 0 Day 1 1 Month A clear clear clear B hazy hazy hazy C clearclear clear D clear clear clear E clear clear clear F clear clear clear*A is unstabilized B contains 2% by weight ofbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate C contains 2%by weight of Instant Example 111 D contains 2% by weight of InstantExample 107 E contains 2% by weight of Instant Example 105 F contains 2%by weight of Instant Example 109

These data show that the instant compounds provide excellent solubilityand compatibility in an alkali-soluble, water-borne acrylic copolymercoating system.

EXAMPLE 115

The hindered amine test stabilizers are incorporated into a coatingsystem as described in Example 113. A 9.5-10 gram sample of each of theliquid coatings is added to a 100 mm×15 mm Petri dish and is placed inan oven at 75 C for 120 minutes. The samples are taken out of the oven,allowed to cool, and are visually observed for clarity over time. Thedevelopment of opacity or haziness is indicative of an incompatibilitybetween the hindered amine stabilizer and the formulated coating.

Solidified Coating in Petri Dish

Sample* 0 Day 1 1 Month A clear clear clear B hazy hazy hazy C clearclear clear D clear clear clear E clear clear clear F clear clear clear*A is unstabilized B contains 2% by weight ofbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate C contains 2%by weight of Instant Example 111 D contains 2% by weight of InstantExample 107 E contains 2% by weight of Instant Example 105 F contains 2%by weight of Instant Example 109

These data show that the instant compounds provide excellent solubilityand compatibility in a two component, water-borne polyurethane coatingsystem.

1. A water compatible or water soluble sterically hindered hydroxysubstituted alkoxyamine compound selected from the group consisting ofcompounds of formulae (8)-(10)

where E is —O-T-(OH)_(b), T is a straight or branched chain alkylene of1 to 18 carbon atoms, cycloalkylene of 5 to 18 carbon atoms,cycloalkenylene of 5 to 18 carbon atoms, a straight or branched chainalkylene of 1 to 4 carbon atoms substituted by phenyl or by phenylsubstituted by one or two alkyl groups of 1 to 4 carbon atoms; b is 1, 2or 3 with the proviso that b cannot exceed the number of carbon atoms inT, and when b is 2 or 3, each hydroxyl group is attached to a differentcarbon atoms of T; E′ is hydrogen, C₁-C₁₈alkyl, C₂-C₁₈alkenyl,C₇-C₁₅phenylalkyl, C₂-C₁₈alkanoyl or phenyl, alkoxy of 1 to 18 carbonatoms, cycloalkoxy of 5 to 12 carbon atoms or aralkoxy of 7 to 15 carbonatoms, or E′ is independently defined as for E, R is hydrogen or methyl,R₆ is hydrogen or C₁-C₆alkyl, R₆′, R₆″ and R₆′″ are independentlydefined as for R₆, R₇ is —N(R₂)(R₂′) or is chlorine, alkoxy of 1 to 12carbon atoms or —N(R₆)(R₆′); or R₇ is

R₈ is defined as for R₇, where one of R₇ and R₈ is —N(R₂)(R₂′); q is 2to 8; X⁻ is an inorganic or organic anion, Y⁺ is a mono-, di- ortri-valent cation, R₂ is glycidyl, C₂-C₁₂alkanoyl substituted by adi(C₁-C₆alkyl)phosphonate, or R₂ is C₂-C₁₂alkyl, C₂-C₁₂alkanoyl orC₇-C₁₈phenylalkyl, each interrupted by one to six oxygen, sulfur or—N(R₆)— groups; C₂-C₁₂alkanoyl, phenyl or C₇-C₁₈phenylalkyl, eachsubstituted by one to six hydroxy groups or by one to six —NHR₆ groups;C₂-C₁₂alkyl substituted by two to six hydroxy groups or by one to six—NHR₆ groups; C₂-C₁₂alkyl, C₂-C₁₂alkanoyl or C₇-C₁₈phenylalkyl, eachinterrupted by one to three —NR₆C(O)— groups; or R₂ is C₁-C₁₂alkyl,C₂-C₁₂alkanoyl, phenyl or C₇-C₁₈phenylalkyl, each substituted by one tothree —SO₃H groups or by one to three —COOR₆ groups; or R₂ is said alkylsubstituted by a piperazine or by a morpholine group; or R₂ is saidinterrupted group further substituted by one to six hydroxy groups or byone to six —NHR₆ groups; or R₂ is said interrupted group furthersubstituted by one to three —SO₃H groups or by one to three —COOR₆groups; or R₂ is C₁-C₁₂alkyl, C₂-C₁₂alkanoyl, phenyl orC₇-C₁₈phenylalkyl, each substituted by one or two —COO⁻Y⁺,—N(R₆)(R₆′)(R₆″)⁺X⁻ or —SO₃ ⁻Y⁺ groups; or R₂ is said C₁-C₁₂alkyl,C₂-C₁₂alkanoyl, phenyl or C₇-C₁₈phenylalkyl, each of which issubstituted by one or two —COO⁻Y⁺, —N(R₆)(R₆′)(R₆″)⁺X⁻ or —SO₃ ⁻Y⁺groups, each further substituted by one or two —OH, —COOR₆ or —NHR₆groups; or R₂ is a mono-valent homo- or co-oligomer consisting ofmonomer units derived from monomers selected from the group consistingof ethylene oxide, propylene oxide, ethylene glycol, propylene glycol,acrylic acid, methacrylic acid, ethylene imine, acrylamide, vinylformamide, vinyl alcohol and vinyl acetate; which homo- or co-oligomerconsists of between 2 and about 24 monomer units and R₂′ is defined asfor R₂ and may also be hydrogen.
 2. A compound according to claim 1wherein T is a straight or branched chain alkylene of 1 to 12 carbonatoms, cycloalkylene of 5 to 12 carbon atoms, cycloalkenylene of 5 to 12carbon atoms, or a straight or branched chain alkylene of 1 to 4 carbonatoms substituted by phenyl or by phenyl substituted by one or two alkylgroups of 1 to 4 carbon atoms.
 3. A compound according to claim 1 whereE is 2-hydroxycyclohexyloxy or 2-hydroxy-2-methylpropoxy.
 4. A compoundaccording to claim 1 of the formula

where E is —O-T(OH)_(b) and where R_(y) is selected from the groupconsisting of —NHCH₂CH₂NHCH₂CH₂NHCH₂CH₂NH₂, —NH₂⁺CH₂CH₂NHCH₂CH₂NHCH₂CH₂NH₂ ⁻OAc, —NHPhSO₃H, —NHPhSO₃ ⁻K⁺, —NHPhSO₃ ⁻Na⁺,—NH₂ ⁺PhSO₃HCl⁻, —NH(3-carboxy-4-chlorophenyl),—NH(3-COO⁻Na⁺-4-chlorophenyl), —NHCH₂CH₂—(N-piperazine), —NH₂⁺CH₂CH₂—(N-piperazine)⁻OAc and —NH₂ ⁺CH₂CH₂—(N-piperazine)⁻Cl.
 5. Astabilized composition comprising an organic material subject to thedeleterious effects of light, heat and oxygen, and an effectivestabilizing amount of a water compatible or water soluble stericallyhindered alkoxyamine or hydroxy substituted alkoxyamine compoundaccording to claim
 1. 6. A composition according to claim 5 which is acoating, ink jet ink, ink jet recording material, photographic recordingmaterial, multi-layer polymer structure, a coextruded film, a radiationcured film, ink or coating; an adhesive or a laminate.
 7. A compositionaccording to claim 5 which additionally comprises an effectivestabilizing amount of at least one coadditive stabilizer selected fromthe group consisting of the phenolic antioxidants, metal stearates,metal oxides, organophosphorus compounds, furanone antioxidants,hydroxylamines, ultraviolet light absorbers, and other hindered aminelight stabilizers.
 8. A composition according to claim 5 whichadditionally comprises an ultraviolet light absorber selected from thegroup consisting of the benzophenones, 2H-benzotriazoles,aryl-s-triazines.
 9. A composition according to claim 5 which is acolored composition containing pigments or dyes.
 10. A compositionaccording to claim 5 which is a colored composition containing dyes. 11.A composition according to claim 5 which is a colored compositioncontaining dyes, which composition is selected from the group consistingof ink jet inks, ink jet recording media, coatings, body care products,household products, textiles and fabrics.
 12. A method for stabilizingink-jet prints, which comprises applying to a recording material forink-jet printing an ink composition containing a water soluble dye or asolution of a dye in an organic solvent and at least one compound of theformulae (8)-(10) as defined in claim 1 and drying said recordingmaterial.
 13. A method for stabilizing ink-jet prints, which comprisesapplying to a recording material for ink-jet printing a casting orcoating dispersion or an aqueous or organic solution containing at leastone compound of the formulae (8)-(10) as defined in claim 1 and furtherapplying either an ink composition containing a water soluble dye or asolution of a dye in an organic solvent; or an ink compositioncontaining a water soluble dye or a solution of a dye in an organicsolvent and at least one compound of the formulae (8)-(10) and dryingsaid recording material.